Metallocene compound, and preparation method therefor and application thereof

ABSTRACT

A metallocene compound having a structure shown by formula (I). A functional group connected to a bridging atom of the metallocene compound is an amine-substituted group and/or a metallocene-substituted group and/or a substituted metallocene group. A metallocene catalyst containing the metallocene compound has high catalytic activity, and can synthesize metallocene polypropylene having high isotacticity. 
       R I R II Z(Cp III ) n (E) 2-n ML IV L V    (I)

The present application claims the priorities of the following patentapplications filed on Oct. 30, 2019:

1. Chinese patent application CN201911047955.1, entitled “Transitionmetal catalyst with unsymmetrically bridged two indenyl groups,preparation method and use thereof”; and

2. Chinese patent application CN201911046672.5, entitled “Siliconbridged metallocene compound, preparation method, and use thereof”,

the entirety of which is incorporated herein by reference.

FIELD OF TECHNOLOGY

The present disclosure is directed to a metallocene compound,preparation method and application thereof, and in particular to ametallocene catalyst containing the metallocene compound, preparationmethod and use of the catalyst. Specifically, the present disclosure isrelated to the technical field of metallocene catalysts.

BACKGROUND

Metallocene polypropylene (mPP) has good utility in fibers, injectionmolding and films, and thus the market demand thereof increases inrecent years. These resin articles have high requirements on thestereoregular structure of polypropylene, and while the structure ofpolypropylene is adjusted and controlled by the structure of thecatalyst.

Metallocene polypropylene with high isotactic structure is an importantresin. Such metallocene polypropylene is synthesized by controlling thegrowth of the propylene chain through the stereo enantiomorphic site ofthe catalyst. The catalyst capable of controlling chain extensionreaction through the stereo enantiomorphic site is required to have a C2axis or a lower C1 axis symmetry (Chem. Rev. 2000, 100, 1223). Thecompounds of Group IV metals such as titanium, zirconium, or hafnium,and bridged diindene ring with racemic structure or derivatives thereofare with this characteristic. In the 1980s, Brintzinger team synthesizedan ethyl diindene ligand with a racemic structure and the later ethylbis(tetrahydroindene) ligand with a racemic structure (J. Organomet.Chem. 1982, 232, 233; 1985, 288, 63). The synthesized titanium andzirconium compounds catalyze propylene to form polypropylene with highisotactic structure under the action of a methylaluminoxane (MAO)additive, whereas the catalyst with meso structure cannot catalyzepropylene to produce polypropylene with high isotacticity. The activityof these racemic catalysts, and the molecular weight and theisotacticity of the products are very sensitive to temperatures. In therange of from −20° C. to 60° C., the difference between the highestactivity (84.43 kg PP/g Zr·h) and the lowest activity (0.88 kg PP)/gZr·h) is nearly two orders of magnitude, the difference between thehighest average molecular weight (300,000 Dalton) and the lowest one(12,000 Dalton) reached 25 times, whereas the molecular weightdistribution of the polymer does not vary very much, which is in therange of from 1.9 to 2.6, and the isotacticity [mmmm] varies within thescope of 86.0-91.0 (Angew. Chem. Int. Ed. Engl. 1985, 24, 507). In 1989,Herrmann et al. synthesized racemic, silicon-based bridged indenezirconium compounds. Subsequently, Spaleck and Herrmann et al. modifiedthe indene ring with substituents. The polypropylene catalyticallyproduced at a higher temperature and under the action of MAO, reaches oralmost reaches the industrial application level in terms of reactivity,molecular weight, molecular weight distribution and isotacticity (up to98%, m.p. 152° C.) (Angew. Chem. Int. Ed. Engl. 1989, 28, 1511; 1992,31, 1348). Since then, a series of Group IV metallocene catalysts ofbridged biindene ring type and its derivative systems have beensuccessively developed and used in isotactic and catalyticpolymerization of propylene (Chem. Rev. 2000, 100, 1253).

Although the reaction conditions such as temperatures, pressures, times,and catalyst concentrations, solvents, auxiliary agents, impurityremoval agents, hydrogen molecular regulators and other factors havegreat influence on the catalytic reaction for generating high isotacticpolypropylene, the adjusting and controlling functions of the stereoenantiomorphic site of the racemic structure play an essential anddecisive role. These structural features are mainly reflected in fiveaspects: an indene ring, a substituent on the indene ring, a bridginggroup, a central metal, and the group which is bonded to the centralmetal and can initiate chain growth. Those skilled in the art are wellaware of the fact that any innovation in one of these five aspects wouldmake the disclosure patentable.

The disclosure in this application mainly focuses on the important roleof bridging groups. The bridging group S′ is referred to as asilicon-containing bridge of 1-4 atoms selected from silanylene,silaalkylene, oxasilanylene, and oxasilaalkylene in the early U.S. Pat.Nos. 5,017,714 and 5,120,867. Subsequently, the U.S. Pat. No. 5,145,819provides a broad definition and patent protection for the bridgingstructure group-(CR⁸R⁹)_(m)—R⁷—(CR⁸R⁹)_(n)—, wherein R⁷ is designated as-M²(R¹¹)(R¹²)—, -M²(R¹¹)(R¹²)-M²(R¹¹)(R²)—, -M²(R¹¹)(R²)—(CR₂ ¹³)—,—O-M²(R¹¹)(R¹²)—O—, —C(R¹¹)(R¹²)—, —O-M²(R¹¹)(R¹²)—, ═BR¹¹, ═AlR¹¹,—Ge—, —Sn—, —O—, —S—, ═SO, ═SO₂, ═NR¹¹, ═CO, ═PR¹¹ or ═P(O)R¹¹, whereinR¹¹, R¹², R¹³ can be identical or different and can be hydrogen, halogenatoms, a C₁-C₁₀ alkyl, C₁-C₁₀ fluoroalkyl, a C₆-C₁₀ aryl, a C₆-C₁₀fluoroaryl, a C₁-C₁₀ alkoxy, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkylgroup, R¹¹ and R¹² as well as R¹¹ and R¹³ are connected with each otherthrough atoms and form a ring; M² is Si, Ge, or Sn; R⁸ and R⁹ can beidentical or different and are defined in the same way as R¹¹; m and ncan be identical or different and are 0, 1, or 2, or m+n is 0, 1, or 2.In these definitions, R⁷ is preferably designated as —C(R¹¹)(R¹²)—,—Si(R¹¹)(R¹²)—, —Ge(R¹¹)(R¹²)—, —O—, —S—, ═SO, ═PR¹¹ or ═P(O)R¹¹. Basedon the disclosure the above, U.S. Pat. No. 5,239,022 further definesthat alkyl refers to linear or branched alkyl, and halogen atom refersto fluorine, chlorine, bromine, and iodine. U.S. Pat. No. 5,239,022 alsogives preferable designations to R¹¹, R¹² and R¹³ groups. For details,please refer to the original disclosure. The definitions of bridginggroups in U.S. Pat. Nos. 5,243,011, 5,276,208, 5,350,817, 5,374,752,5,483,002, 5,672,668, 5,714,427, 5,741,868, 6,087,291, 6,114,479,6,124,230, 6,228,795B1, and US2003/0088022A1 are similar to the above.In U.S. Pat. No. 5,770,753, the bridging group is directly defined asR³, which specially includes the following: -M²(R¹⁴)(R¹⁵)—,-M²(R¹⁴)(R¹⁵)-M²(R¹⁴)(R¹⁵)—, —C(R¹⁴)(R¹⁵)—C(R¹⁴)(R¹⁵)—,—O-M²(R¹⁴)(R¹⁵)—O—, —C(R¹⁴)(R¹⁵)—, —O-M²(R¹⁴)(R¹⁵)—,—C(R¹⁴)(R¹⁵)-M²(R¹⁴R¹⁵)—, —C(R¹⁴)(R¹⁵)—C(R¹⁴R¹⁵)—C(R¹⁴)(R¹⁵)—, ═BR¹⁴,═AlR¹⁴, —Ge—, —O—, —S—, ═SO, ═SO₂, ═NR¹⁴, ═CO, ═PR¹⁴, or ═P(O)R¹⁴,wherein R¹⁴ and R¹⁵ can be identical or different, and can be hydrogen,halogen atoms, C₁-C₁₀ alkyl, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ alkoxy, C₆-C₁₀aryl, C₆-C₁₀ fluoroaryl, C₆-C₁₀ phenolic group, C₂-C₁₀ alkenyl, C₇-C₄₀arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or R¹⁴ and R¹⁵ areconnected each other through atom(s) and form one or more rings; M² isSi, Ge, or Sn. Subsequent patents, U.S. Pat. Nos. 5,786,432, 5,380,821,5,840,644, 5,840,948, 5,852,142, 5,929,264, 5,932,669, 6,051,522, U.S.60/517,272, U.S. Pat. Nos. 6,057,408, 6,242,544B1, 6,255,506B1,6,376,407B1, U.S. 63/764,408B1, U.S. 63/764,409B1, U.S. 63/764,410B1,U.S. 63/764,411B1, U.S. 63/764,412B1, US2001/0021755A1, US2006/016490A1,and US2006/0252637A1 all refer to similar or substantially the samebridging group structures. In U.S. 63/764,413B1, the bridging group isdefined as biphenyl M²(C₆R¹⁷R¹⁸R¹⁹R²⁰—C₆R²¹R²²R²³R²⁴)—, and the overalldefinitions of R¹⁷ to R²⁴ are designated as R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, are connected eachother through atoms and form one or more rings, and R¹⁷ to R²⁴ arepreferably H. R¹ and R² can be the same or different. They are one of H,C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₁₀ aryl, C₆-C₁₀ phenol, C₂-C₁₀ alkenyl,C₇-C₄₀ arylalkyl, C₂-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, OH, a halogenatom, or conjugated diene (randomly substituted with one or morehydrocarbyl groups), three-carbon hydrogen silicon group or three-carbonhydrogen group, three-carbon hydrogen silicon substituted hydrocarbylgroup (wherein the number of non-hydrogen atoms is up to 30). Suchpatents include U.S. Pat. Nos. 5,616,747, 6,376,627B1, 6,380,120B1,6,380,121B1, 6,380,122B1, 6,380,123B1, 6,380,124B1, 6,380,130B1,6,380,130B1, 6,380,134B1, etc. U.S. Pat. Nos. 5,391,790 and 5,616,747directly indicate the bridging group with —R⁶—, which is defined as-[M²(R⁸)(R⁹)]_(p)—, wherein M² is C, Si, Ge, or Sn; R⁸ and R⁹ can be thesame or different, and are designated as H, C₁-C₂₀ alkyl, C₆-C₁₄ aryl,C₁-C₁₀ alkoxy, C₂-C₁₀ alkenyl, C₇-C₂₀ arylalkyl, C₇-C₂₀ alkylaryl,C₆-C₁₀ phenol, C₁-C₁₀ fluoroalkyl, C₆-C₁₀ haloaryl, C₂-C₁₀ alkynyl,—SiR⁷ ₃, halogen, or five-membered or six-membered heteroaromaticradical (containing one or more heteroatoms), and are connected byatom(s) to form one or more rings; p is 1, 2, or 3. U.S. Pat. No.5,739,366 defines bridging group Y, which is designated as divalentC₁-C₂₀ hydrocarbyl groups, divalent C₁-C₂₀ halogenated hydrocarbylgroups, divalent silicon-containing groups, divalentgermanium-containing groups, and divalent tin-containing groups, —O—,—CO—, —S—, —SO—, —SO₂—, —NR⁵—, —P(R⁵)—, —P(O)(R⁵)—, —BR⁵— or —AlR⁵— (R⁵is H, a halogen atom, C₁-C₂₀ hydrocarbyl group, divalent C₁-C₂₀halogenated hydrocarbyl group). In U.S. Pat. Nos. 6,218,558, 6,252,097B1and 6,255,515B1 submitted by Japan Polymer Chemical Company, the benzenering in the indene ring is expanded to a seven-membered ring, and thecorresponding bridging group Q is defined as a divalent C₁-C₂₀hydrocarbyl group, a divalent C₁-C₂₀ halogenated group, a silylenecontaining a C₁-C₂₀ hydrocarbyl group or a C₁-C₂₀ halogenatedhydrocarbyl group, an oligosilylenyl group containing a C₁-C₂₀hydrocarbyl group or a C₁-C₂₀ halogenated hydrocarbyl group, or agermanenyl group containing a C₁-C₂₀ hydrocarbyl group or a C₁-C₂₀halogenated hydrocarbyl group, and connects with two five-memberedrings. In U.S. Pat. Nos. 6,444,606B1, 7,342,078B2 and US2003/0149199A1,the bridging group R⁹ is defined as —O-M²(R¹⁰)(R¹¹)—O—, —C(R¹⁰)(R¹¹)—,—O-M²(R¹⁰)(R¹¹)—, —C(R¹⁰)(R¹¹)-M²(R¹⁰R¹¹)—, -M²(R¹⁰)(R¹¹)—,-M²(R¹⁰)(R¹¹)-M²(R¹⁰)(R¹¹)—, —C(R¹⁰)(R¹¹)—C(R¹⁰)(R¹¹)—,-M²(R¹⁰)(R¹¹)—[C(R¹⁰R¹¹)]_(x)-M²(R¹⁰)(R¹¹)—,—C(R¹⁰)(R¹¹)—C(R¹⁰R¹¹)—C(R¹⁰)(R¹¹)—, >BR¹⁰, >AlR¹⁰, —Ga—, —O—, —S—, >SO,>SO₂, >NR¹⁰, >CO, >PR¹⁰, >P(O)R¹⁰ or >R(O)R¹⁰, wherein R¹⁰ and R¹¹ canbe the same or different and are hydrogen, a halogen atom, or C₁-C₄₀group, such as C₁-C₂₀ alkyl, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ alkoxy, C₆-C₁aryl, C₆-C₁₀ fluoroaryl, C₆-C₁₀ phenol, C₂-C₁₀ alkenyl, C₇-C₄₀arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or R¹⁰ and R¹¹ areconnected each other through atom(s) and form one or more rings, and M²is Si, Ge, or Sn.

The bridging group connects with two cyclopentadienyl groups, indenylgroups or fluorenyl groups. That is, the two groups are stericallydefined. This bridging enhances the rigidity of the ligand structure andplays an important role in the formation of racemic structurecharacteristic of catalysts. The catalyst with the racemic structure canadjust and control the chain growth of the stereo enantiomorphic sitesof propylene well and then produce metallocene polypropylene with highisotacticity.

Although many bridged metallocene catalysts have been reported, not manyof them have industrial applications or application prospects. Becauseindustrial applications have high requirements on the isotacticity ofmetallocene polypropylene. For example, the metallocene polypropyleneproduced by some companies, can only be used in resin products when itsisotacticity [mmmm] is greater than 97%. China's polypropylene productsare generally produced by using traditional Natta type catalysts. Someof these catalysts are added with simple metallocene compoundcomponents. There are nearly no reports on complete use of metallocenecompounds as catalysts because of theoretical and technical difficultiesin this regard.

China's polypropylene products are basically produced by usingtraditional supported Ziegler-Natta catalysts. There are few reports onthe use of bridged two-group metallocene catalysts to control theproduction of polypropylene with high isotacticity because there arestill technical difficulties in this regard.

SUMMARY

A first technical problem to be solved by the present disclosure is thatthe metallocene catalyst in the prior art has the technical problem thatthe activity is not high enough, to provide a new metallocene compound,wherein the group connecting to the bridge atom of the metallocenecompound is a group substituted by an amino group, and/or a groupsubstituted by a metallocene group and/or a substituted metallocenegroup. The special structure endows a high catalytic activity for themetallocene catalyst containing the metallocene compound; furthermore,with the metallocene catalyst, a high-regularity metallocenepolypropylene can be synthesized.

A second technical problem to be solved by the present disclosure is toprovide a preparation method of the metallocene compound for solving thefirst technical problem.

A third technical problem to be solved by the present disclosure is toprovide a metallocene catalyst adopting the metallocene compound forsolving the first technical problem.

A fourth technical problem to be solved by the present disclosure is toprovide a preparation method of the catalyst for solving the thirdtechnical problem above.

A fifth technical problem to be solved by the present disclosure is toprovide use of the metallocene compound the first technical problemabove or the catalyst for solving the third technical problem.

In order to solve the first technical problem above, the presentdisclosure adopts a technical solution as follows.

Provided is a metallocene compound, having a structure as shown informula (I):

R^(I)R^(II)Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V)   formula (I)

wherein in formula (I), R¹ and R¹¹ are the same or different, and atleast one of R^(I) and R^(II) is selected from amino-substituted C₁-C₂₀hydrocarbyl, amino-substituted C₁-C₂₀ halohydrocarbyl, amino-substitutedC₁-C₂₀ alkoxy and amino-substituted C₆-C₂₀ phenolic group; and/or atleast one of R^(I) and R^(II) is selected from metallocenegroup-substituted C₁-C₂₀ hydrocarbyl, metallocene group-substitutedC₁-C₂₀ halohydrocarbyl, metallocene group-substituted C₁-C₂₀ alkoxy, andmetallocene group-substituted C₆-C₂₀ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene groups substituted byC₁-C₂₀ hydrocarbyl, C₁-C₂₀ halohydrocarbyl, C₁-C₂₀ alkoxy or C₆-C₂₀phenolic group;

Z is selected from carbon, silicon, germanium, and tin;

Cp^(III) is cyclopentadienyl containing or not containing a substituent,indenyl containing or not containing a substituent, or fluorenylcontaining or not containing a substituent, as shown in formula (II),wherein R^(i), R^(ii), and R^(iii) are the substituents in thecorresponding rings;

R^(i), R^(ii) and R^(iii) are the same or different, and eachindependently selected from hydrogen, and linear or branched, saturatedor unsaturated C₁-C₂₀ hydrocarbyl with or without a heteroatom;

E is NR^(iv) or PR^(iv);

R^(iv) is selected from hydrogen and linear or branched, saturated orunsaturated C₁-C₂₀ hydrocarbyl, with or without a heteroatom;

M is selected from IVB group metals;

L^(IV) and L^(V) are the same or different, and each independentlyselected from hydrogen and linear or branched, saturated or unsaturatedC₁-C₂₀ hydrocarbyl with or without a heteroatom; and

n is 1 or 2.

According to the present disclosure, when n is 1, Cp^(III) is any one ofthe above cyclopentadienyl, indenyl, or fluorenyl; when n is 2, Cp^(III)is two of the above cyclopentadienyl, two of the above indenyl, or twoof the above fluorenyl, or Cp^(III) is two of the abovecyclopentadienyl, indenyl, or fluorenyl. When n is 2, the two Cp^(III)groups can be are the same or different.

According to a preferred embodiment of the present disclosure, the aminois as shown in formula (III):

wherein in formula (III), R_(a) and R_(b) are the same or different, andeach independently selected from hydrogen, C₁-C₆ alkyl, C₆-C₁₈ aryl,C₇-C₂₀ arylalkyl, and C₇-C₂₀ alkylaryl, preferably C₁-C₆ alkyl, C₆-C₁₂aryl and C₇-C₁₀ arylalkyl, and more preferably C₁-C₄ alkyl, phenyl andC₇-C₉ arylalkyl.

According to a preferred embodiment of the present disclosure, the metalin the metallocene group is Fe, and preferably, the metallocene group isferrocenyl.

According to a preferred embodiment of the present disclosure, informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from amino-substituted C₁-C₁₀hydrocarbyl, amino-substituted C₁-C₁₀ halohydrocarbyl, amino-substitutedC₁-C₁₀ alkoxy and amino-substituted C₆-C₁₀ phenolic group; and/or atleast one of R^(I) and R^(II) is selected from metallocenegroup-substituted C₁-C₁₀ hydrocarbyl, metallocene group-substitutedC₁-C₁₀ halohydrocarbyl, metallocene group-substituted C₁-C₁₀ alkoxy andmetallocene group-substituted C₆-C₁₀ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene groups substituted byC₁-C₁₀ hydrocarbyl, C₁-C₁₀ halohydrocarbyl, C₁-C₁₀ alkoxy or C₆-C₁₀phenolic group.

According to a preferred embodiment of the present disclosure, informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from amino-substituted C₁-C₆hydrocarbyl, amino-substituted C₁-C₆ halohydrocarbyl, amino-substitutedC₁-C₆ alkoxy, and amino-substituted C₆-C₈ phenolic group; and/or atleast one of R^(I) and R^(II) is selected from metallocenegroup-substituted C₁-C₆ hydrocarbyl, metallocene group-substituted C₁-C₆halohydrocarbyl, metallocene group-substituted C₁-C₆ alkoxy, andmetallocene group-substituted C₆-C₈ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene groups substituted byC₁-C₆ hydrocarbyl, C₁-C₆ halohydrocarbyl, C₁-C₆ alkoxy or C₆-C₈ phenolicgroup.

According to a preferred embodiment of the present disclosure, informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from amino-substituted C₁-C₆hydrocarbyl; and/or at least one of R^(I) and R^(II) is selected frommetallocene group-substituted C₁-C₆ hydrocarbyl; and/or at least one ofR^(I) and R^(II) is selected from metallocene group substituted by C₁-C₆hydrocarbyl.

According to a preferred embodiment of the present disclosure, informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from amino-substituted C₁-C₆ linearalkyl; and/or at least one of R^(I) and R^(II) is selected frommetallocene group-substituted C₁-C₆ linear alkyl; and/or at least one ofR^(I) and R^(II) is selected from metallocene group-substituted by C₁-C₆linear alkyl.

According to a preferred embodiment of the present disclosure, informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from substituted byamino-substituted C₁-C₄ linear alkyl; and/or at least one of R^(I) andR^(II) is selected from metallocene group-substituted C₁-C₄ linearalkyl; and/or at least one of R^(I) and R^(II) is selected frommetallocene groups substituted by C₁-C₄ linear alkyl.

According to a preferred embodiment of the present disclosure, when onlyone group of R^(I) and R^(II) is selected from the groups as definedabove, the other group can be selected from C₁-C₂₀ hydrocarbyl, C₁-C₂₀halohydrocarbyl, C₁-C₂₀ alkoxy and C₆-C₂₀ phenolic group, preferablyC₁-C₁₀ hydrocarbyl, C₁-C₁₀ halohydrocarbyl, C₁-C₁₀ alkoxy and C₆-C₁₀phenolic group, more preferably C₁-C₆ hydrocarbyl, C₁-C₆halohydrocarbyl, C₁-C₆ alkoxy and C₆-C₈ phenolic group, and furtherpreferably C₁-C₆ hydrocarbyl.

According to the present disclosure, R^(i), R^(ii), and R^(iii) refer tothe substituents on the corresponding rings in the above formula. WhenCp^(III) is a cyclopentadienyl group, one or up to four R^(i) canindependently connect to the cyclopentadienyl group at any one, two,three, or all four positions (without selection) of the cyclopentadienylgroup; when Cp^(III) is an indenyl group, one or two R^(i) canindependently connect to the indenyl group at one of two positions ofthe five-membered ring or at all two positions without selection; one tofour R^(ii) can independently connect to the indenyl group at one, two,three, or all four positions (without selection) of the four positionsin the six-membered ring; when the benzene ring on which R^(iii) is apart of the indenyl ring, the definition of R^(iii) is the same asR^(ii); when Cp^(III) is a fluorenyl group, one to four R^(ii) and oneto four R^(iii) can independently connect the respective six-memberedring at any one, two, three or all four positions in the twosix-membered rings. R^(i), R^(ii), and R^(iii) each independently referto hydrogen, linear or branched C₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀aryl, C₇-C₂₀ alkylaryl, or C₇-C₂₀ arylalkyl groups, these groupsoptionally contain one or more heteroatoms, and can also be saturated orunsaturated. R^(i), R^(ii), and R^(iii) may form a saturated orunsaturated cyclic groups, and these groups may optionally contain oneor more heteroatoms.

According to a preferred embodiment of the present disclosure, informula (II), R^(i), R^(ii) and R^(iii) are the same or different, eachindependently selected from hydrogen, C₁-C₂₀ hydrocarbyl, C₁-C₂₀haloalkyl, C₆-C₂₀ aryl, C₆-C₂₀ haloaryl, C₇-C₄₀ arylalkyl, C₇-C₄₀alkylaryl, C₃-C₂₀ cycloalkyl, C₃-C₂₀ heterocycloalkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₁-C₂₀ alkoxy, C₆-C₂₀ phenolic group, C₁-C₂₀ amino and agroup containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, informula (II), R^(i), R^(ii) and R^(iii) are the same or different, andeach independently selected from hydrogen, C₁-C₁₀ hydrocarbyl, C₁-C₁₀haloalkyl, C₆-C₁₀ aryl, C₆-C₁₀ haloaryl, C₇-C₂₀ arylalkyl, C₇-C₂₀alkylaryl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ heterocycloalkyl, C₂-C₁₀ alkenyl,C₂-C₁₀ alkynyl, C₁-C₁₀ alkoxy, C₆-C₁₀ phenolic group, C₁-C₁₀ amino and agroup containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, informula (II), R^(i), R^(ii) and R^(iii) are the same or different, andeach independently selected from hydrogen, C₁-C₆ hydrocarbyl, C₁-C₆haloalkyl, C₆-C₆ aryl, C₆-C₆ haloaryl, C₇-C₁₀ arylalkyl, C₇-C₁₀alkylaryl, C₃-C₆ cycloalkyl, C₃-C₆ heterocycloalkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, C₁-C₆ alkoxy, C₆-C₆ phenolic group, C₁-C₆ amino and agroup containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, informula (I), R^(iv) selected from hydrogen and linear or branched,saturated or unsaturated C₁-C₁₀ hydrocarbyl with or without aheteroatom.

According to a preferred embodiment of the present disclosure, informula (I), R^(iv) selected from hydrogen and linear or branched,saturated or unsaturated C₁-C₆ hydrocarbyl with or without a heteroatom.

According to a preferred embodiment of the present disclosure, informula (I), M is selected from Ti, Zr and Hf.

According to a preferred embodiment of the present disclosure, informula (I), M is Zr.

According to a preferred embodiment of the present disclosure, L^(IV)and L^(V) are the same, and selected from hydrogen, chlorine, methyl,phenyl, benzyl and dimethylamino.

In order to solve the second technical problem, the present disclosureadopts any one of the following technical solutions.

Option 1:

A preparation method of the metallocene compound as mentioned above,

when n is 2, the preparation method comprises:

S1. reacting a H₂(Cp^(III)) with an alkali metal-organic compound toform a corresponding [H(Cp^(III))]⁻ alkali metal salt;

S2. reacting the [H(Cp^(III))]⁻ alkali metal salt with a R^(I)R^(II)ZX₂to form a R^(I)R^(II)Z[H(Cp^(III))]₂;

S3. reacting the R^(I)R^(II)Z[H(Cp^(III))]₂ with an alkali metal-organiccompound to form a corresponding R^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metalsalt;

S4. reacting the R^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metal salt with anX₂ML^(IV)L^(V) for salt elimination reaction, to obtain aR^(I)R^(II)Z(Cp^(III))₂ML^(IV)L^(V);

when n is 1, the preparation method comprises:

S1. reacting a H₂(Cp^(III)) and a H₂(E) with an alkali metal-organiccompound respectively, to form a corresponding [H(Cp^(III))]⁻ alkalimetal salt and a corresponding [H(E)]⁻ alkali metal salt;

S2. reacting the [H(Cp^(III))]⁻ alkali metal salt and the [H(E)] alkalimetal salt with a R^(I)R^(II) ZX₂ to form aR^(I)R^(II)Z[H(Cp^(III))][H(E)];

S3. reacting the R^(I)R^(II)Z[H(Cp^(III))][H(E)] with an alkalimetal-organic compound to form a correspondingR^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt;

S4. reacting the R^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt with anX₂ML^(IV)L^(V) for salt elimination reaction, to obtain aR^(I)R^(II)ZCp^(III) EML^(IV)L^(V).

wherein X is selected from Cl, Br and I;

-   -   preferably, in S4, R^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metal salt        or R^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt directly reacts        with X₂ML^(IV)L^(V) for salt elimination reaction without        separation.

Option 2:

A preparation method of the metallocene compound as mentioned above,comprising:

preparing the metallocene compound by carrying out a Z hydrogenationreaction between a precursor R^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V)and a precursor of the R^(II);

wherein the precursor of the R^(II) is a molecule containing a multiplebond, preferably, the molecule containing a multiple bond is selectedfrom organic multiple bond molecules, CO and CO₂, wherein the multiplebond is selected from Groups 13 to 16 elements of the same or differentatoms, preferably is one or more bonds of C═C, C═C, C═N, CEN, C═O, C═P,N═N, C═S, C═C═C, C═C═N, C═C═O, and N═C═N.

According to the present disclosure, the above metallocene compound canbe prepared by both options 1 and 2.

According to a preferred embodiment of the present disclosure, theabove-mentioned metallocene compound is prepared by option 2. That is,the above-mentioned metallocene compound is prepared by additionreaction of the precursor R^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V),R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) orH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and the molecule containingmultiple bonds Z—H. Collins reported the step-by-step synthesis ofMeHZ(Cp)₂Zr(NMe₂)₂ and MeHZ(Ind)₂Zr(NMe₂)₂ (Macromolecules 2001, 34,3120), that is, the dimer ligands MeHZ(CpH)₂ and MeHZ(IndH)₂ areprepared respectively, and then react with Zr(NMe₂)₄ to generateMeHZ(Cp)₂Zr(NMe₂)₂ and MeHZ(Ind)₂Zr(NMe₂)₂. This method is similar tothe synthesis method as described in the background art wherein a protonof metallocenel ring or non-metallocene compound is removed. The twocompounds were reacted with excess Me₃ZCl to obtain the compoundsMeHZ(Cp)₂ZrCl₂ and MeHZ(Ind)₂ZrCl₂.

For the preparation of the precursorsR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V),R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) orH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V), the technical solution adoptedin the present disclosure can use this method, and can also use the saltelimination method as mentioned in the background art, but the one-potmethod is preferred. The present disclosure provides a specificimplementation of the one-pot method, and when the selected rawmaterials change, the implementation process of the one-pot method doesnot change.

When n is 2, R^(I)HZX₂ is selected to react with two moles of theH(Cp^(III)) alkali metal salt (when the H(Cp^(III)) is two differentgroups, each is one mole). The H(Cp^(III)) alkali metal salt is preparedby reacting a ligand H₂ (Cp^(III)) with an equivalent amount of analkali metal-organic compound. The alkali metal-organic compound isselected from the group consisting of metal hydride, metal alkyl,alkenyl metal, aryl metal, and amine metal, and preferably metal alkyl;the alkali metal is selected from Li, Na, and K, preferably Li; X isselected from Cl, Br, and I, preferably Cl. The generatedR^(I)HZ[H(Cp^(III))]₂ does not need to be separated and is directly usedin the next reaction. There are two schemes as follows.

a) R^(I)HZ[H(Cp^(III))]₂ is reacted with L^(vii)L^(viv)ML^(IV)L^(V) foreliminating a stable small molecule HL^(viii) or HL^(viv) to obtainR^(I)HZ(Cp^(III))₂ML^(IV)L^(V), L^(viii) and L^(viv) are leaving groups,which can be the same or different, and selected from hydrogen, alkyl,aryl, amine. Preferably L^(viii) and L^(viv) are the same, and selectedfrom methyl, phenyl and dimethylamino groups.

b) R^(I)HZ[H(Cp^(III))]₂ is reacted with two moles of an alkalimetal-organic compound to form an alkali metal salt, wherein thedefinition of the alkali metal-organic compound is the same as above;and then the alkali metal salt is reacted with an X₂ML^(IV)L^(V) saltfor salt elimination to obtain R^(I)HZ(Cp^(III))₂ML^(IV)L^(V), wherein Xhas the same definition as above.

When n is 1, R^(I)HZX₂ is selected to react with one mole of H(CP^(III))alkali metal salt and one mole of H(E) alkali metal salt. Thepreparation of H(Cp^(II)I) alkali metal salt is the same as that ofH(E). The alkali metal salt is prepared by reacting H₂(E) with anequivalent amount of an alkali metal-organic compound, and thedefinition of the alkali metal-organic compound is the same as above.The generated R^(I)HZ[H(Cp^(III))][H(E)] does not need to be separatedand is directly used in the next reaction. There are two schemes asfollows:

a) R^(I)HZ[H(Cp^(III))][H(E)] is reacted withL^(viii)L^(viv)ML^(IV)L^(V)V for eliminating a stable small moleculeHL^(viii) or HL^(viv) to obtain R^(I)HZ(Cp^(III))(E)M^(IV)L^(V), whereinL^(viii) and L^(viv) are defined as above.

b) R^(I)HZ[H(Cp^(III))][H(E)] is reacted with two moles of an alkalimetal-organic compound to form an alkali metal salt, wherein thedefinition of the alkali metal-organic compound is the same as above;and then the alkali metal salt is reacted with an X₂ML^(IV)L^(V) saltfor salt elimination to obtain R^(I)HZ(Cp^(III))₂ML^(IV)L^(V), wherein Xhas the same definition as above.

Selecting R^(II) HZX₂ to prepare R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) or selecting H₂ZX₂ to prepareH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) is similar to the above schemes.

During the preparation of R^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V),R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) orH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V), the reaction is carried out inan aprotic solvent The solvent is selected from linear or branchedalkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds,halogenated hydrocarbon compounds, ether compounds and cyclic ethercompounds, preferably toluene, xylene, chlorobenzene, heptane,cyclohexane, methylcyclohexane, dichloromethane, chloroform,tetrahydrofuran, ether and dixoane. Among them, H₂(Cp^(III)), H₂(E),R^(I)HZ[H(Cp^(III))]₂, R^(II) HZ[H(Cp^(III))]₂, H₂Z[H(Cp^(III))]₂,R^(I)HZ[H(Cp^(III))][H(E)], R^(II) HZ[H(Cp^(III))][H(E)] orH₂Z[H(Cp^(III))][H(E)] is reacted with the alkali metal-organic compoundat a temperature of −60 to 140° C., the preferred temperature range is−20 to 110° C.; the reaction time is greater than 0.016 h, and thepreferred range of the reaction time is 2-100 h. The reaction ofR^(I)HZX₂, R^(II) HZX₂, H₂ZX₂ with H(Cp^(III)) or H(E) alkali metalsalt, and the reaction of X₂ML^(IV)L^(V) with R^(I)HZ[(Cp^(III))]₂,R^(II) HZ[(Cp^(III))]₂, H₂Z[(Cp^(III))]₂, R^(I)HZ[(Cp^(III))][(E)],R^(II) HZ[(Cp^(III))][(E)] or H₂Z[(Cp^(III))][(E)]alkali metal salt arecarried out at a temperature of −75 to 100° C., preferably thetemperature range is −75 to 60° C.; and the reaction time is greaterthan 0.1 h, and preferably the reaction time range is 6-100 h. Thereaction of R^(I)HZ[H(Cp^(III))]₂, R^(II)HZ[H(Cp^(III))]₂,H₂Z[H(Cp^(III))]₂, R^(I)HZ[H(Cp^(III))][H(E)], R^(II)HZ[H(Cp^(III))][H(E)], or H₂Z[H(Cp^(III))][H(E)] withL^(viii)L^(viv)ML^(IV)L^(V) for eliminating a small molecule is carriedout at a temperature of 0 to 160° C., and the preferred temperaturerange is 20 to 140° C.; and the reaction time is greater than 0.1 h, andpreferably, the reaction time is in the range of 2-100 h.

The technical solution further provided by the present disclosure ispreparing (I) by Z—H addition reaction between the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V),R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) orH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and a molecule containing amultiple bond. In the molecule containing a multiple bond, the multiplebond is selected from elements of groups 13 to 16, which may be the samekind of atoms or different kinds of atoms, preferably C═C, C═C, C═N,C═N, C═O, C═P, N═N, C═S, C═C═C, C═C═N, C═C═O, N═C═N. The Z—H additionreaction requires the participation of a catalyst. The catalyst isselected from transition metal catalysts and Lewis acid catalysts,preferably platinum catalysts of the transition meta catalysts andB(C₆F₅)₃ catalysts of the Lewis acids. In order to better achieve thepurpose of the present disclosure, a catalyst that preferably has noeffect on L^(IV) and L^(V) in the aforementioned precursor or does notaffect the reaction of Z—H with multiple bonds is required. This meansthat when the catalyst interacts with the L^(IV) and L^(LV) in theaforementioned precursors and affects the addition reaction of Z—H withmultiple bonds, the L^(IV) and L^(LV) groups need to undergo a groupconversion reaction through the prepared related compounds. It isconverted into a group that does not affect the reaction of Z—H withmultiple bond. For example, when L^(IV) and L^(V) are methy, theB(C₆F₅)₃ catalyst will complex with the methyl to form [MeB(C₆F₅)₃], andthus lose the catalytic effect. Then L^(IV) and L^(V) need to beconverted to NMe₂ or other non-reactive group.

The reaction of Z—H in the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V), R^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) orH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) with the molecule containing amultiple bond is carried out in a protic solvent. The solvent may beselected from linear or branched alkane compounds, cycloalkanecompounds, aromatic hydrocarbon compounds, halogenated hydrocarboncompounds, ether compounds and cyclic ether compounds, preferablytoluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane,dichloromethane, chloroform, tetrahydrofuran, ether and dioxane. Theamount of catalyst used in the reaction is 0.00001-50% preferably0.01-20% of the total mass of the reactants; the reaction is carried outat a temperature of −30 to 140° C., and the preferred temperature rangeis 0 to 90° C.; the reaction time is more than 0.1 h, and the reactiontime is preferably in the range of 2-50 h. The target product (I) isseparated or purified by recrystallization.

According to the present disclosure, “Z” is preferably silicon.

According to a preferred embodiment of the present disclosure, the Zhydrogenation reaction is carried out in the presence of a catalystselected from transition metal catalysts and Lewis acid catalysts,preferably platinum catalysts of transition metal catalysts and B(C₆F₅)₃of Lewis acid catalysts.

According to a preferred embodiment of the present disclosure, theamount of the catalyst used in the Z hydrogenation reaction is0.00001-50%, preferably 0.01-20% of the total mass of the reactants.

According to a preferred embodiment of the present disclosure, thetemperature of the Z hydrogenation reaction is −30 to 140° C.,preferably 0 to 90° C.

According to a preferred embodiment of the present disclosure, thereaction time of the Z hydrogenation reaction is greater than 0.1 h,preferably 2-50 h.

According to a preferred embodiment of the present disclosure, theobtained precursor is separated or purified by recrystallization, andthe solvent for the recrystallization is an aprotic solvent; preferably,it is selected from linear or branched alkane compounds and cycloalkanecompounds, aromatic hydrocarbon compounds, halogenated hydrocarboncompounds, ether compounds and cyclic ether compounds; furtherpreferably, selected from toluene, xylene, hexane, heptane, cyclohexaneand methylcyclohexane.

According to a preferred embodiment of the present disclosure, theprecursor R^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) is prepared by aone-pot method of chemical reaction.

According to a preferred embodiment of the present disclosure, when n is2, the preparation method of the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) comprises:

step 1), reacting a H₂(Cp^(III)) with an alkali metal-organic compoundto form a corresponding [H(Cp^(III))] alkali metal salt;

step 2), reacting the [H(Cp^(III))]⁻ alkali metal salt with a R^(I)HZX₂to form a R^(I)HZ[H(Cp^(III))]₂;

step 3), directly reacting the R^(I)HZ[H(Cp^(III))]₂ without separation,with a L^(viii)L^(viv)ML^(IV)L^(V) for eliminating a stable smallmolecule L^(viii) or L^(viv), to obtain the precursorR^(I)HZ(Cp^(III))₂ML^(IV)L^(V),

and/or, directly reacting the R^(I)HZ[H(Cp^(III))]₂ without separation,with an alkali metal-organic compound to form an alkali metal salt; theobtained alkali metal salt is then reacted with an X₂ML^(IV)L^(V) forsalt elimination reaction, to obtain the precursorR^(I)HZ(Cp^(III))₂ML^(IV)L^(V); and

when n is 1, the preparation method of the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) comprises:

step 1), reacting a H₂(Cp^(III)) and a H₂(E) respectively with an alkalimetal-organic compound to form a corresponding [H(Cp^(III))]⁻ alkalimetal salt and a corresponding [H(E)]⁻ alkali metal salt;

step 2), reacting the [H(Cp^(III))]⁻ alkali metal salt and the [H(E)]⁻alkali metal salt with R^(I)HZX₂ to form a R^(I)HZ[H(Cp^(III))][H(E)];

step 3), directly reacting the R^(I)HZ[H(Cp^(III))][H(E)] withoutseparation, with a L^(viii)L^(viv)ML^(IV)L^(V) by eliminating a stablesmall molecule L^(viii) or LV^(viv), to obtain the precursorR^(I)HZCp^(III)EML^(IV)L^(V);

and/or, directly reacting the R^(I)HZ[H(Cp^(III))][H(E)] withoutseparation, with an alkali metal-organic compound to form an alkalimetal salt; then reacting the obtained alkali metal salt with aX₂ML^(IV)L^(V) for salt elimination reaction, to obtain the precursorR^(I)HZCp^(III)EML^(IV)L^(V);

wherein X is selected from Cl, Br and I.

According to the present disclosure, when one pot method is used, R^(I)is formed by the addition reaction of the Z—H bond in the precursorR^(II)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and the multiple bond in amolecule containing multiple bond, and R^(II) is formed by the additionreaction of the Z—H bond in the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and a multiple bond in amolecule containing multiple bond, or both R^(I) and R^(II) are formedby the addition reaction of Z—H bond in the precursorH₂Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and a multiple bond in a moleculecontaining multiple bond; the multiple bond molecule is an organicmultiple bond molecule, CO or CO₂, preferably an organic multiple bondmolecule. Thus, R^(I) and R^(II) can be the same or different.

According to a preferred embodiment of the present disclosure, in eachstep, a reaction temperature of the reaction is −100° C. to 140° C.,preferably −85° C. to 110° C.; and/or, ae reaction time is greater than0.016 h, preferably 2 to 100 h.

According to a preferred embodiment of the present disclosure, in eachstep, the reaction materials are mixed at −100° C. to −20° C.,preferably −85° C. to −10° C., react at 10° C. to 50° C., preferably 20°C. to 35° C. for 1 h to 100 h, preferably 5 h to 50 h.

According to a preferred embodiment of the present disclosure, in eachstep, the reaction is carried out in an aprotic solvent selected fromlinear or branched alkane compounds, cycloalkane compounds, aromaticcompounds, halogenated hydrocarbon compounds, ether compounds and cyclicether compounds, preferably toluene, xylene, chlorobenzene, heptane,cyclohexane, methylcyclohexane, dichloromethane, chloroform,tetrahydrofuran, ether and dioxane.

According to a preferred embodiment of the present disclosure, thealkali metal-organic compound selected from hydrogenated metal, alkylmetal, alkenyl metal, aromatic metal and amine metal, preferably alkylmetal, and more preferably C₁-C₆ alkyl metal.

According to a preferred embodiment of the present disclosure, thealkali metal is selected from Li, Na and K, preferably Li.

In order to solve the third technical problem, the present disclosureadopts the following technical solution.

A catalyst for α-olefin polymerization reaction, comprising: themetallocene compound as mentioned above or the metallocene compoundprepared according to the above preparation method, a cocatalyst and acarrier.

According to a preferred embodiment of the present disclosure, thecocatalyst is selected from one or more of a Lewis acid and an ioniccompound containing a non-coordination anion and a Lewis acid orcontaining a non-coordination anion and a Bronsted acid cation;preferably, the Lewis acid comprises one or more of alkyl aluminum,alkyl aluminoxane and organic borides; and/or the ionic compoundcontaining a non-coordination anions and a Lewis acid or containing anon-coordination anion and a Bronsted acid cation is selected fromcompounds containing 1-4 perfluoroaryl substituted borate anions.

According to a preferred embodiment of the present disclosure, the alkylaluminum includes trimethyl aluminum, triethyl aluminum, triisopropylaluminum, tri-n-propyl aluminum, tri-isobutyl aluminum, tri-n-butylaluminum, tri-isoamyl aluminum, tri-n-amyl aluminum, tri-isohexylaluminum, tri-isoheptyl aluminum, tri-n-heptyl aluminum, tri-isooctylaluminum, tri-n-octyl aluminum, tri-isononyl aluminum, tri-n-nonylaluminum, tri-isodecyl aluminum and tri-n-decyl aluminum; and/or thealkyl aluminoxane includes methyl aluminoxane, ethyl aluminoxane andbutyl modified aluminoxane; and/or the organic boride includestrifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris(pentafluorophenyl) borane, tris (3,5-difluorophenyl) borane and tris(2,4,6-trifluorophenyl) borane.

According to a preferred embodiment of the present disclosure, the alkylaluminum comprises trimethyl aluminum and triethyl aluminum.

According to a preferred embodiment of the present disclosure, theperfluoroaryl group is selected from perfluorophenyl, perfluoronaphthyl, perfluoro biphenyl and perfluoroalkyl phenyl, and the cationis selected from N, N-dimethylphenylammonium ion, triphenylcarbooniumion, trialkyl ammonium ion and triarylammonium ion.

According to a preferred embodiment of the present disclosure, thecontent of the metallocene compound in the catalyst is 0.001 mass % to10 mass %, preferably 0.01 mass % to 1 mass %, based on M element;and/or the molar ratio of Al element in the cocatalyst to M element inthe metallocene compound is (1-500):1, preferably (50-300):1

According to a preferred embodiment of the present disclosure, thecatalyst has an asymmetric structure. The asymmetric structure can bemulti-layered, which can refer to the asymmetry of R^(I) and R^(II) inmetallocene compounds, the asymmetric structure formed by theinteraction between metallocene compounds and additives, or the carrierloading after the interaction between metallocene compounds andadditives to further strengthen the asymmetry.

In order to solve the fourth technical problem above, the technicalsolution adopted by the present disclosure is as follows.

A method for preparing the above-mentioned catalyst includes: combiningthe metallocene compound, the co-catalyst and the carrier under theaction of a solvent to form the catalyst.

According to a preferred embodiment of the present disclosure, theconditions of the combination include: the temperature of thecombination is −40° C. to 200° C., preferably 40° C. to 120° C.; thetime of the combination is greater than 0.016 h, preferably 2 h-100 h.

According to a preferred embodiment of the present disclosure, thesolvent is selected from linear hydrocarbons, branched hydrocarbons,cyclic saturated hydrocarbons and aromatic hydrocarbons, preferablytoluene, xylene, n-butane, n-pentane, isopentane, neopentane,cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane,methylcyclohexane, petroleum ether, isoheptane, and neoheptane.

According to a preferred embodiment of the present disclosure, thepreparation method of the above-mentioned catalyst comprises:

i) mixing the co-catalyst, the carrier and the solvent to obtain amixture A;

ii) mixing the mixture A with the metallocene compound to obtain amixture B; preferably, mixting the metallocene compound in a solventfirst, to form a mixture which is then mixed with the mixture A;

iii) separating a solid from the mixture B, and drying the solid toprepare the catalyst.

According to a preferred embodiment of the present disclosure, in stepi), the carrier is calcinated. Preferably, conditions of the calcinationtreatment include: a calcination temperature of 50° C. to 700° C., and acalcination time of 0.5 h to 240 h.

According to a preferred embodiment of the present disclosure, themixture A is heated. Preferably, conditions of the heating treatmentinclude: a heating temperature of 30° C. to 110° C., and a heating timeof 0.1 h to 100 h.

According to a preferred embodiment of the present disclosure, in stepiii), conditions of the drying treatment include: a drying temperatureof 30° C. to 110° C., and a drying time of 0.1 h to 100 h.

According to a preferred embodiment of the present disclosure, the solidis washed before the drying treatment, preferably the solid is washedwith the solvent, and more preferably, the solvent after washing iswashed until the solvent does not contain metal ions.

In order to solve the fifth technical problem above, the technicalsolution adopted by the present disclosure is as follows.

Use of the above-mentioned metallocene compound or the metallocenecompound prepared according to the above-mentioned preparation method orthe above-mentioned catalyst or the above-mentioned preparation methodin the field of α-olefin polymerization.

According to a preferred embodiment of the present disclosure,polymerization reaction of the α-olefin is carried out in the presenceof the above-mentioned metallocene compound or the metallocene compoundprepared according to the above-mentioned preparation method or theabove-mentioned catalyst or the above-mentioned preparation method, toobtain poly-α-olefin.

According to a preferred embodiment of the present disclosure, thepolymerization reaction is carried out under a solvent-free condition.

According to a preferred embodiment of the present disclosure,conditions of the polymerization reaction include: a reactiontemperature of −50° C. to 200° C., preferably 30° C. to 100° C.; and areaction time of 0.01 h to 60 h, preferably 0.1 h to 10 h.

According to a preferred embodiment of the present disclosure, themetallocene catalyst or metallocene catalyst system is used in an amountof 0.001 mg to 1000 mg, preferably 0.01 mg to 200 mg, and morepreferably 0.1 mg to 20 mg per gram of α-olefin.

According to a preferred embodiment of the present disclosure, theα-olefin includes C₂-C₂₀ α-olefin, preferably C₂-C₁₄ α-olefin, morepreferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene and 1-eicosene, preferably 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene.

In some specific embodiments of the present disclosure, the α-olefin ispropylene. When the α-olefin is propylene, the bulk polymerizationreaction can be carried out with propylene and hydrogen as raw materials(this bulk polymerization reaction can be carried out in a tank reactoror a tubular reactor; it can be carried out batchwise or continuously),the amount of hydrogen can be 0 to 0.10 g/g propylene, preferably0.00001 to 0.10 g/g propylene. In addition, when polymerizing propylene,impurity breakers can be used. The impurity breaker is a substancecommonly used in the field, and its specific dosage can be 0-100 mmol/gpropylene, preferably 0.001-10 mmol/g propylene.

In some specific embodiments of the present disclosure, the α-olefin isethylene. When the α-olefin is ethylene, the gas phase polymerizationreaction is carried out, and the reaction temperature is 0-200° C.,preferably 20-140° C.; and/or, the reaction time is 0.016-60 h,preferably 0.1-20 h; and/or, ethylene The pressure is 0.1-15 MPa,preferably 0.2-10 MPa, and/or the amount of catalyst is 0.00001-100 mg/gethylene, and/or the amount of impurity removal agent is 0-100 mmol/gethylene, and/or hydrogen The dosage is 0-0.01 g/g ethylene.

According to some embodiments of the present disclosure, the impurityremoving agent is selected from alkyl aluminum compounds, aromaticaluminum compounds, aluminoxane compounds, borohydride compounds, alkylmagnesium compounds, aromatic magnesium compounds, alkyl zinc compounds,aromatic zinc compound, alkyl lithium compound, aromatic lithiumcompound, alkyl sodium compound, aromatic sodium compound, alkylpotassium compound and aromatic potassium compound; preferably, selectedfrom trimethyl aluminum, triethyl aluminum, trimethyl aluminum Isobutylaluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum, methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxaneand modified aluminoxane, alkyl aluminum halides, dimethyl magnesium,diethyl magnesium, di-n-butyl magnesium, dimethyl zinc, diethyl zinc,di-n-butyl zinc, methyl lithium, n-butyl lithium and tert-butyl lithium.

In the present disclosure, the term “hydrocarbyl” may be alkyl, aryl,alkylaryl, arylalkyl, alkynyl, alkenyl and the like.

In the present disclosure, the term “heteroatom” may refer to aheteroatom such as oxygen, sulfur, nitrogen, and phosphorus.

In the present disclosure, the term “substituted” may refer tosubstitution by a substituent, which may be selected from halogens,non-carbon oxo acid groups and their derivatives, and optionallysubstituted alkyl, aralkyl and aryl groups. For example, a groupsubstituted with an alkyl group, an aryl group, an amino group, ahydroxyl group, an alkoxy group, a carbonyl group, an oxa group, acarboxyl group, a thia group, a sulfur oxyacid, a halogen group, and acombination thereof.

In the present disclosure, the term “one-pot method” may refer to acontinuous multi-step synthesis reaction carried out in the samereactor.

In the present disclosure, “Me” means methyl: “Et” means ethyl; “iPr”means isopropyl; “tBu” means tert-butyl; “iBu” means isobutyl; “iPr”Means isopropyl; “Ph” means phenyl; “Fc” means CpFe(C₅H₄); “Flu” meansfluorenyl.

In the present disclosure, “Tol” means toluene.

The beneficial effects of the present disclosure are at least:

1) At least one of the two different groups on the bridging atom of themetallocene compound used in the present disclosure is an aminesubstituted group and/or a metallocene substituted group and/or asubstituted metallocene group, and thus it can promote the formation ofa metallocene catalyst with a racemic structure. When combined with aco-catalyst and a carrier, it can realize the chain growth of olefinssuch as propylene and ethylene that is controlled by the stereoenantiomorphic sites to form high isotacticity metallocene polypropyleneor metallocene polyethylene.

2) The method for preparing metallocene compounds provided by thepresent disclosure can effectively carry out group transformations ofbridging atoms, and prepare bridging metallocene compounds with variousstructures and compositions. The bridged metallocene compound obtainedafter the hydrogenation of the bridged atom is combined with thecocatalyst and the carrier to form a metallocene catalyst, which hasgood thermal stability and catalytic activity, and can be used for thepolymerization of ethylene or propylene and other alpha-olefins.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present disclosure will be further illustrated by the followingexamples.

In the following embodiments, unless otherwise specified, thealuminum/zirconium ratio is the molar ratio of aluminum to zirconium.

In the present disclosure, unless otherwise specified, the Al/Zr ratiorefers to the molar ratio of Al element to Zr element.

In the present disclosure, unless otherwise specified, “%” means masspercentage.

In the present disclosure, the calculation formula of polymerizationactivity is: Polymerization activity=quality of polymerizedproduct/(polymerization time×catalyst amount×zirconium content).

A. Preparation of Metallocene Compounds Synthesis Example 1

Preparation of the metallocene compound as shown in formula 1:

40 mmol of 4-phenyl-2-methylindene was weighed and dissolved in 200 mLof Et₂O, and cooled to −78° C. 40 mmol of n-butyllithiumin in a hexanesolution with a concentration of 2.4M was slowly dropwise added into theresulting mixture over 15 min. After the addition was completed, themixture was naturally warmed to room temperature under stirring, andstirred for another 12 hours at room temperature to obtain a solution ofindenyl lithium compound.

20 mmol of Me(PhMeNH₂CH₂CH₂C)SiCl₂ was weighed and dissolved in 100 mLof n-hexane, and cooled to −78° C. The solution of indenyl lithiumcompound prepared above was slowly dropwise added into the resultingmixture over 30 minutes. Then the mixture was naturally warmed to roomtemperature under stirring, and stirred for another 12 h at roomtemperature. The insoluble matter was removed by filtration, and thefiltrate was passed through a silica gel column to obtain a yellowsolution. The solvent was drained to obtain a yellow compoundMe(PhMeNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₅)₂, which was weighed 8.2 mmol, andthe yield was 41%.

5 mmol of Me(PhMeNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₅)₂ was weighed and dissolvedin 100 mL THF, and cooled to −78° C. 10 mmol of n-butyllithiumin in ahexane solution with a concentration of 2.4M was slowly dropwise addedinto the resulting mixture over 15 minutes. The resulting mixture wasnaturally warmed to room temperature under stirring, and stirred at roomtemperature for another 12 hours to obtain a solution of silicon-bridgedindenyl lithium compound.

5 mmol ZrCl₄ was weighed and added into 100 mL THF, and cooled to −78°C. With stirring, the solution of silicon-bridged indenyl lithiumcompound prepared above was slowly dropwise added into the resultingmixture over 15 minutes. The resulting mixture was then naturally warmedto room temperature under stirring, and stirred for another 12 h at roomtemperature. The insoluble matter was removed by filtration, thefiltrate was collected, and the THF solvent in the filtrate was removed.The remaining solid was extracted with 100 mL of toluene. The extractionsolution was crystallized at −20° C. to obtain an orange-red zirconocenecompound [Me(PhMeNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂]ZrCl₂ as shown in formula1, which was weighed 1.2 mmol, and the yield was 24%.

The preparation methods of the metallocene compounds of formula 2 toformula 11 were similar to this, except that, Me(PhMeNH₂CH₂CH₂C)SiCl₂ inthe second step was replaced with Me(PhMeNH₂CH₂CH₂CH₂C)SiCl₂,Me(Me₂NH₂CH₂CH₂CH₂C)SiCl₂, Me(Me₂NH₂CH₂C)SiCl₂, Me(Me₂NH₂CH₂CH₂C)SiCl₂,Me(NH₂Pr₂NH₂CH₂CH₂C)SiCl₂, Me(iPr₂NH₂CH₂CH₂C)SiCl₂,Me(iBuMeNH₂CH₂CH₂C)SiCl₂, Me(iBuEtNH₂CH₂CH₂C)SiCl₂,Me(iPrEtNH₂CH₂CH₂C)SiCl₂, (Me₂NH₂CH₂C)(iBuMeNH₂CH₂CH₂C)SiCl₂respectively, finally to obtain zirconocene compoundsMe(PhMeNH₂CH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 2, which wasweighed 1.0 mmol, yield 20%),Me(Me₂NH₂CH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 3, which wasweighed 1.4 mmol, yield 28%),Me(Me₂NH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂(formula 4, which was weighed 1.2mmol, yield 24%), Me(Me₂NH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 5,which was weighed 1.0 mmol, yield 20%),Me(NH₂Pr₂NH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 6, which wasweighed 1.3 mmol, yield 26%), Me(iPr₂NH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂(formula 7, which was weighed 1.0 mmol, yield 20%),Me(iBuMeNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 8, which was weighed0.9 mmol, yield 18%), Me(iBuEtNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂(formula 9, which was weighed 0.8 mmol, yield 16%),Me(iPrEtNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 10, which wasweighed 0.9 mmol, yield 18%),(Me₂NH₂CH₂C)(iBuMeNH₂CH₂CH₂C)Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 11, whichwas weighed 0.6 mmol, yield 12%) respectively.

The preparation methods of the metallocene compound of formula 12 toformula 14 were also the similar to this, except thatMe(PhMeNCH₂CH₂CH₂)SiCl₂ in the second step was replaced withMe[CpFe(C₅H₄)CH₂CH₂]SiCl₂, Me[CpFe(C₅H₄)CH₂CH₂CH₂]SiCl₂,Me[CpFe(C₅H₄)CH₂]SiCl₂ respectively, and finally zirconocene compoundsMe[CpFe(C₅H₄)CH₂CH₂]Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 12, which wasweighed 1.0 mmol, yield 20%),Me[CpFe(C₅H₄)CH₂CH₂CH₂]Si(4-Ph-2-MeC₉H₄)₂ZrCl₂ (formula 13, which wasweighed 1.3 mmol, yield 26%), Me[CpFe(C₅H₄)CH₂]Si(4-Ph-2-MeC₉H₄)₂ZrCl₂(formula 14, which was weighed 0.8 mmol, yield 16%) were obtained.

The preparation methods of the metallocene compound of formula 15 wasthe similar to this, except that, 4-phenyl-2-methyl indenyl in the firststep was replaced with 4-(4-tert butyl)phenyl-2-methyl indenyl, and inthe meantime, Me(PhMeNCH₂CH₂CH₂)SiCl₂ in the second step was replacedwith Me[CpFe(C₅H₄)CH₂CH₂]SiCl₂, finally to obtain zirconocene compoundMe[CpFe(C₅H₄)CH₂CH₂]Si(4-(4-tBuC₆H₄)-2-MeC₉H₄)₂ZrCl₂ (formula 15, whichwas weighed 1.0 mmol, yield 20%).

Synthesis Examples 2-12 Preparation of Precursor Preparation of HydrogenSilicon Bridged Bisindenyl Zirconocene CompoundMeHSi(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (MS-1)

2-methyl-7-p-tert-butylphenylindene (5.24 g, 20 mmol) was weighed anddissolved in Tol (80 mL) solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol)was slowly dropwise added into the mixture at −78° C., gradually warmedto room temperature and reacted overnight to obtain a wine-red solution.Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added intothe mixture at −78° C., and gradually warmed to room temperature andstirred for more than 8 hours to obtain a yellow suspension. The yellowsuspension was placed at −78° C., and n-butyllithium (2.4M, 8.5 mL, 20mmol) was slowly dropwise added into the mixture. After warmed to roomtemperature, stirring was continued for 2 h to obtain an orange-yellowturbid solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glovebox was put into a vial. followed by adding 40 mL of toluene, and beingplaced under the nitrogen protection, and was added into the aboveyellow turbid liquid at room temperature. Soon the color would graduallydarken from orange-yellow to brown-black. Reaction was carried out for 1day. The reaction solution was filtered under the protection ofnitrogen, the obtained filtrate was drained of solvent, washed withn-hexane, filtered and drained to obtain a yellow solid. The yellowsolid was recrystallized from toluene in multiple steps at −20° C. toobtain 1.76 g (24.2%) of racemic compound rac-MS-1 and 3.42 g (47.0%) ofmeso-MS-1 compound.

The two compounds were isomers and had the same elemental composition.One of them was selected to be elementally analyzed to confirm itscomposition. The composition was C₄₁H₄₈Cl₂SiZr(Mr=731.04): theoreticalvalue: C, 67.36; H, 6.62; measured value: C, 67.54, H, 6.56.

Synthesis Example 2 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(Me₂NCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1a)

Rac-MS-1 (1.45 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. Me₂NCH═CH₂ (0.156 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1 mmol,5% dosage) were added into the mixture. The mixture was heated to 50° C.for 24 h. All the volatile components were removed by vacuuming at roomtemperature. The remaining solid was washed with a small amount(approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was driedunder vacuum for 6 hours to obtain 1.36 g (85.2%) of yellow solidrac-MS-1a.

The composition was C₄₅H₅₇Cl₂NSiZr(Mr=802.16): theoretical value: C,67.38; H, 7.16; N, 1.75; measured value: C, 67.42; H, 7.19; N, 1.78.

Synthesis Example 3 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(Me₂NCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (meso-MS-1a)

The implementation steps were the same as Synthesis Example 2, whereinrac-MS-1 was replaced with meso-MS-1 (1.45 g, 2 mmol), and finally 1.4 g(87.7%) of yellow solid meso-MS-1a was obtained.

The compound meso-MS-1 and the above-mentioned rac-MS-1 were isomers,and the composition was also C₄₅H₅₇Cl₂NSiZr(Mr=802.16): theoreticalvalue: C, 67.38; H, 7.16; N, 1.75; measured value: C, 67.44; H, 7.18; N,1.77.

Synthesis Example 4 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconium CompoundMe(PhMeNCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1b)

The implementation steps were the same as Synthesis Example 2, whereinMe₂NCH═CH₂ was replaced with PhMeNCH═CH₂ (0.293 g, 2.2 mmol), andfinally 1.65 g (95.9%) of yellow solid rac-MS-1b was obtained.

The composition was C₅₀H₅₉Cl₂NSiZr(Mr=864.23): theoretical value: C,69.49; H, 6.88; N, 1.62; measured value: C, 69.45; H, 6.89; N, 1.65.

Synthesis Example 5 Preparation of Aminoalkyl-Containing Silicon BridgedBis-Indenocyl Zirconocene CompoundMe(Me₂NCH₂CH₇CH)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1c)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with Me₂NCH₂CH═CH₂ (0.187 g, 2.2 mmol), and finally 1.35 g(83.2%) of yellow solid rac-MS-1c was obtained.

The composition was C₄₆H₅₉Cl₂NSiZr(Mr=816.18): theoretical value: C,67.69; H, 7.29; N, 1.72; measured value: C, 67.65; H, 7.30; N, 1.70.

Synthesis Example 6 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(PhMeNCH₂CH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1d)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with PhMeNCH₂CH═CH₂ (0.324 g, 2.2 mmol), and finally 1.61 g(92.3%) of yellow solid rac-MS-1d was obtained.

The composition was C₅₁H₆₁Cl₂NSiZr(Mr=878.25): theoretical value: C,69.75; H, 7.00; N, 1.59; measured value: C, 69.78; H, 7.02; N, 1.60.

Synthesis Example 7 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(iPr₂NCH₂CH₇CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1e)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with iPr₂NCH₂CH═CH₂ (0.310 g, 2.2 mmol), and finally ayellow solid rac-MS-1e 1.54 g (88.8%) was obtained.

The composition was C₅₀H₆₇Cl₂NSiZr(Mr=872.29): theoretical value: C,68.85; H, 7.74; N, 1.61; measured value: C, 68.83; H, 7.71; N, 1.63.

Synthesis Example 8 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(iBuMeNCH₂CH₂CH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1f)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with iBuMeNCH₂CH₂CH═CH₂ (0.310 g, 2.2 mmol), and finally ayellow solid rac-MS-if 1.57 g (90.62%) was obtained.

The composition was C₅₀H₆₇Cl₂NSiZr(Mr=872.29): theoretical value: C,68.85; H, 7.74; N, 1.61; measured value: C, 68.82; H, 7.72; N, 1.63.

Synthesis Example 9 Preparation of Aminoalkyl-Containing Silicon BridgedBisindenyl Zirconocene CompoundMe(PhMeNCH₂CH₂CH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₁₂ (rac-MS-1g)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with PhMeNCH₂CH₂CH═CH₂ (0.354 g, 2.2 mmol), and finally ayellow solid rac-MS-1 g 1.64 g (92.52%) was obtained.

The composition was C₅₂H₆₃Cl₂NSiZr(Mr=892.28): theoretical value: C,70.00; H, 7.12; N, 1.57; measured value: C, 70.04; H, 7.11; N, 1.59.

Synthesis Example 10 Preparation of Aminoalkyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(iPrEtNCH₂CH₂CH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1h)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with iPrEtNCH₂CH₂CH═CH₂ (0.310 g, 2.2 mmol), and finally ayellow solid rac-MS-1h 1.57 g (90.61%) was obtained.

The composition was C₅₀H₇₁Cl₂NSiZr(Mr=876.32): theoretical value: C,68.53; H, 8.17; N, 1.60; measured value: C, 68.51; H, 8.18; N, 1.62.

Synthesis Example 11 Preparation of Ferrocenylalkenyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(FcCH═CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1i)

The implementation steps were the same as Example 1, wherein Me₂NCH═CH₂was replaced with FcC≡CH (0.420 g, 2 mmol), and finally an orange-redsolid rac-MS-1i 1.72 g(91.98%) was obtained. In FcC≡CH, Fc=CpFe(C₅H₄).

The composition was C₅₃H₅₈Cl₂FeSiZr(Mr=941.09): theoretical value: C,67.64; H, 6.21; measured value: C, 67.71; H, 6.25.

Synthesis Example 12 Preparation of Ferrocenylalkenyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(FcCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂ZrCl₂ (rac-MS-1j)

The implementation steps were the same as in Example 1, whereinMe₂NCH═CH₂ was replaced of FcCH═CH₂ (0.424 g, 2 mmol), and finally anorange-red solid rac-MS-1j 1.63 g(87.17%). In FcCH═CH₂, Fc=CpFe(C₅H₄).

The composition was C₅₃H₆₀Cl₂FeSiZr(Mr=943.10): theoretical value: C,67.50; H, 6.41; measured value: C, 67.53; H, 6.43.

Synthesis Examples 13 and 14 Preparation of Precursors Preparation ofHydrogen Silicon Bridged Bisindenyl Zirconocene CompoundMeHSi(2-Me-7-p-tBuC₆H₄C₉H₄)₂Zr(NMe₂)₂ (rac-MS-2)

2-methyl-7-p-tert-butyl phenylindene (5.24 g, 20 mmol) was weighed anddissolved in tol (160 ml) solvent. N-butyl lithium (2.4 M, 8.5 ml, 20mmol) was slowly dropwise added into the mixture at −78° C. Aftergradually warmed to the room temperature, the resulting mixture wasreacted overnight to obtain a wine red solution. Methyldichlorosilane(1.04 ml, 10 mmol) was slowly dropwise added into the wine red solutionat 78° C., followed by gradually warming to the room temperature andstirring for more than 8 hours to obtain a yellow suspension. The yellowsuspension was filtered and LiCl precipitation was removed to obtain ayellow solution. tetramethylaminozirconium (2.68 g, 10 mmol) was addedinto the yellow solution under stirring, and heated to 70 to 100° C. for12 hours. When it was cooled to room temperature, the volatilecomponents were removed, and the remaining solid was recrystallized withtoluene and hexane to obtain 4.83 g (64.9%) of orange crystalline solidrac-ms-2.

The composition was C₄₅H₆₀N₂SiZr(Mr=748.28): theoretical value: C,72.23; H, 8.08; N, 3.74; measured value: C, 72.21; H, 8.05; N, 3.76.

Synthesis Example 13 Preparation of Aminoalkyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(PhMeNCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂Zr(NMe₂) (rac-MS-2a)

Rac-MS-2 (1.49 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeNCH═CH₂ (0.293 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain an orange solid rac-MS-2a 1.62g (92.2%).

The composition was C₅₄H₇₁N₃SiZr(Mr=881.47): theoretical value: C,73.58; H, 8.12; N, 4.77; measured value: C, 73.60; H, 8.14; N, 4.75.

Synthesis Example 14 Preparation of Ferrocenylalkenyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(FcCH₂CH₂)Si(2-Me-7-p-tBuC₆H₄C₉H₄)₂Zr(NMe₂)₂ (rac-MS-2b)

The implementation steps were the same as Example 13, whereinPhMeNCH═CH₂ was replaced with FcCH═CH₂ (0.424 g, 2 mmol), and finally anorange-red solid meso-MS-1a 1.4 g(87.7%). In FcCH═CH₂, Fc=CpFe(C₅H₄).

The composition was C₅₇H₇₂N₂FeSiZr(Mr=960.35): theoretical value: C,71.29; H, 7.56; N, 2.93; measured value: C, 71.27; H, 7.56; N, 2.91.

Synthesis Examples 15 and 16 Preparation of Precursors Preparation ofHydrogen Silicon-Based Bridged Bisindenyl Zirconocene CompoundMeHSi(2-Me-7-PhC₉H₄)₂ZrCl₂ (MS-3)

2-methyl-7-phenylindene (4.13 g, 20 mmol) was weighed and dissolved inTol (160 mL) solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowlydropwise added into the mixture at −78° C., gradually warmed to roomtemperature and reacted overnight to obtain a wine-red solution.Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added intothe solution at −78° C., and then gradually warmed to room temperatureand stirred for more than 8 hours to obtain a yellow suspension. Theyellow suspension was placed at −78° C., and n-butyllithium (2.4M, 8.5mL, 20 mmol) was slowly dropwise added into the suspension. Afterwarming to room temperature, stirring was continued for 2 h to obtain anorange-yellow turbid solution. Zirconium tetrachloride (2.33 g, 10 mmol)from a glove box was put into a vial, followed by adding 40 mL oftoluene, and being placed under the nitrogen protection. Zirconiumtetrachloride was added into the above yellow turbid liquid at roomtemperature, and soon the color would gradually darken fromorange-yellow to brown-black. Reaction was carried out for 1 day. Thereaction solution was filtered under the protection of nitrogen, theobtained filtrate was drained of solvent, washed with n-hexane, filteredand drained to obtain a yellow solid. The yellow solid wasrecrystallized from toluene in multiple steps at −20° C. to obtain 1.25g (18.7%) of the racemic compound rac-MS-3 and 2.75 g (41.2%) of themeso-MS-3 compound.

The composition was C₃₃H₂₈Cl₂SiZr(Mr=614.79): theoretical value: C,64.47; H, 4.59; measured value: C, 64.48; H, 4.61.

Synthesis Example 15 Preparation of Aminoalkyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(PhMeNCH₂CH₂)Si(2-Me-7-PhC₉H₄)₂ZrCl₂ (rac-MS-3a)

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeNCH═CH₂ (0.293 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.41 g (87.4%) orange-redsolid rac-MS-3a.

The composition was C₄₂H₃₉Cl₂NSiZr(Mr=747.98): theoretical value: C,67.44; H, 5.26; N, 1.87; measured value: C, 67.42; H, 5.27; N, 1.86.

Synthesis Example 16 Preparation of Ferrocenylalkenyl-Containing SiliconBridged Bisindenyl Zirconocene CompoundMe(FcCH₂CH₂)Si(2-Me-7-PhC₉H₄)₂ZrCl₂ (rac-MS-3b)

The implementation steps were the same as Synthesis Example 13, whereinPhMeNCH═CH₂ was replaced with FcCH═CH₂ (0.424 g, 2 mmol), and finally anorange-red solid rac-MS-3b 1.53 g (86.7%) was obtained. In FcCH═CH₂,Fc=CpFe(C₅H₄).

The composition was C₄₅H₄₀Cl₂FeSiZr(Mr=826.86): theoretical value: C,65.37: H, 4.88; measured value: C, 65.36; H, 4.89.

Preparation of Precursors of Synthesis Examples 16 and 17 Preparation ofHydrogen Silicon Bridged Bisfluorenyl Zirconocene CompoundMeHSiFlu₂ZrCl₂(MS-4)

Fluorene (3.32 g, 20 mmol) was weighed and dissolved in Tol (160 mL)solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwiseadded into the mixture at −78° C. Then the resulting mixture wasgradually warmed to room temperature and reacted overnight to obtainwine red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowlyadded dropwise into the wine red solution at −78° C., and graduallywarmed to room temperature and stirred for more than 8 hours to obtain ayellow suspension. The yellow suspension was placed at −78° C., andn-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added intoit. After warming to room temperature, stirring was continued for 2 h toobtain an orange-yellow turbid solution. Zirconium tetrachloride (2.33g, 10 mmol) from a glove box was put into a vial, followed by adding 40mL of toluene, and being placed under the nitrogen protection. Zirconiumtetrachloride was added into the above yellow turbid liquid at roomtemperature, and soon the color would gradually darken fromorange-yellow to brown-black. Reaction was carried out for 1 day. Thereaction solution was filtered under the protection of nitrogen, theobtained filtrate was drained of solvent, washed with n-hexane, filteredand drained to obtain a yellow solid. The yellow solid wasrecrystallized from toluene at −20° C. to obtain 3.89 g (72.8%) ofcompound MS-4.

The composition was C₂₇H₂₀Cl₂SiZr(Mr=534.66): theoretical value: C,60.66; H, 3.77; measured value: C, 60.64; H, 3.74.

Synthesis Example 17 Preparation of Aminoalkyl-Containing SiliconBridged Bisferrocenyl Zirconocene Compound Me(PhMeNCH₂CH₂)SiFlu₂ZrCl₂(MS-4a)

MS-4 (1.07 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent.PhMeNCH═CH₂ (0.293 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1 mmol, usageof 5%) were added into the mixture, heated to 50° C. and reacted for 24h. All the volatile components were removed by vacuuming at roomtemperature, and the remaining solid was washed with a small amount(approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was driedin vacuum for 6 hours to obtain of orange solid MS-4a 1.21 g (90.6%).

The composition was C₃₆H₃Cl₂NSiZr(Mr=667.85): theoretical value: C,64.74; H, 4.68; N, 2.10; measured value: C, 64.73; H, 4.71; N, 2.11.

Synthesis Example 18 Preparation of Ferrocenyl-Containing Alkyl SiliconBridged Bisfluorenyl Zirconocene Compound Me(FcCH₂CH₂)SiFlu₂ZrCl₂(MS-4b)

The implementation steps were the same as Synthesis Example 17, whereinPhMeNCH═CH₂ was replaced with FcCH═CH₂ (0.424 g, 2 mmol), and finally anorange-red solid MS-4b 1.32 g (88.4%) was obtained. In FcCH═CH₂,Fc=CpFe(C₅H₄).

The composition was C₃₉H₃₂Cl₂FeSiZr(Mr=746.73): theoretical value: C,62.73; H, 4.32; measured value: C, 62.72; H, 4.31.

Synthesis Example 19 Preparation ofMe[(PhMeN(CH₂)₅)]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeN(CH₂); CH═CH₂ (0.388 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g,0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.49 g (86.2%) of orange-redsolid rac-MS-3c.

The composition was C₄₅H₄₅Cl₂NSiZr(Mr=790.97): theoretical value: C,68.41; H, 5.74; N, 1.77; measured value: C, 68.44; H, 5.75; N, 1.76.

Synthesis Example 20 Preparation ofMe[PhMeN(CH₂)₈]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeN(CH₂)₆CH═CH₂ (0.480 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g,0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.57 g (86.3%) of orange-redsolid rac-MS-3d.

The composition was C₄₈H₅₁Cl₂NSiZr(Mr=832.15): theoretical value: C,69.28; H, 6.18; N, 1.68; measured value: C, 69.25; H, 6.16; N, 1.70.

Synthesis Example 21 Preparation ofMe[PhMeN(CH₂)₁₂]Si(2-Me-7-PhC₉H₄)ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeN(CH₂)₉CH═CH₂ (0.573 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g,0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.72 g (89.9%) of orange-redsolid rac-MS-3e.

The composition was C₅₁H₅₇Cl₂NSiZr(Mr=874.23): theoretical value: C,70.07; H, 6.57; N, 1.60; measured value: C, 70.04; H, 6.55; N, 1.60.

Synthesis Example 22 Preparation ofMe[PhMeN(CH₂)₁₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. PhMeN(CH₂)₁₂CH═CH₂ (0.666 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g,0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.83 g (91.2%) of orange-redsolid rac-MS-3f.

The composition was C₅₄H₃Cl₂NSiZr(Mr=916.31): theoretical value: C,70.78; H, 6.93; N, 1.53; measured value: C, 70.76; H, 6.95; N, 1.52.

Synthesis Example 23 Preparation ofMe[p-ClC₆H₄MeN(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. p-ClC₆H₄MeN(CH₂)₃CH═CH₂ (0.461 g, 2.2 mmol) and B(C₆F₅)₃ (0.051g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C.and reacted for 24 h. All the volatile components were removed byvacuuming at room temperature, and the remaining solid was washed with asmall amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times.It was dried in vacuum for 6 hours to obtain 1.62 g (90.0%) oforange-red solid rac-MS-3 g.

The composition was C₄₅H₄₄Cl₃NSiZr(Mr=824.51): theoretical value: C,65.55; H, 5.38; N, 1.70; measured value: C, 65.56; H, 5.36; N, 1.72.

Synthesis Example 24 Preparation ofMe[p-MeOC₆H₄MeN(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. p-MeOC₆H₄MeN(CH₂)₃CH═CH₂ (0.454 g, 2.2 mmol) and B(C₆F₅)₃(0.051 g, 0.1 mmol, usage of 5%) was added into the mixture, heated to50° C. and reacted for 24 h. All the volatile components were removed byvacuuming at room temperature, and the remaining solid was washed with asmall amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times.It was dried in vacuum for 6 hours to obtain 1.60 g (89.2%) oforange-red solid rac-MS-3h.

The composition was C₄₆H₄₆Cl₂NOSiZr(Mr=819.09): theoretical value: C,67.45; H, 5.66; N, 1.71; measured value: C, 67.47; H, 5.63; N, 1.72.

Synthesis Example 25 Preparation of Me[Fc(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. Fc(CH₂)₃CH═CH₂ (0.559 g, 2.2 mmol) (note: Fc=CpFe(C₅H₄)) andB(C₆F₅)₃ (0.051 g, 0.1 mmol, 5% usage) were added into the mixture,heated to 50° C. and reacted for 24 h. All the volatile components wereremoved by vacuuming at room temperature, and the remaining solid waswashed with a small amount (approximately 1.5 mL each time) n-hexane for2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.67 g(87.9%) of orange-red solid rac-MS-3i.

The composition was C₄₈H₄₆Cl₂FeSiZr(Mr=868.95): theoretical value: C,66.35; H, 5.34; measured value: C, 66.36; H, 5.33.

Synthesis Example 26 Preparation of Me(Fc(CH₂)₈)Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. Fc(CH₂)₆CH═CH₂ (0.652 g, 2.2 mmol)(note: Fc=CpFe(C₅H₄)) andB(C₆F₅)₃ (0.051 g, 0.1 mmol, 5% usage) were added into the mixture,heated to 50° C. and reacted for 24 h. All the volatile components wereremoved by vacuuming at room temperature, and the remaining solid waswashed with a small amount (approximately 1.5 mL each time) n-hexane for2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.72 g(86.3%) of orange-red solid rac-MS-3j.

The composition was C₅₁H₅₂Cl₂FeSiZr(Mr=911.03): theoretical value: C,65.55; H, 5.38; measured value: C, 65.56; H, 5.37.

Synthesis Example 27 Preparation of Me[Fc(CH₂)₁₂]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. Fc(CH₂)₁₀CH═CH₂ (0.775 g, 2.2 mmol) (note: Fc=CpFe(C₅H₄)) andB(C₆F₅)₃ (0.051 g, 0.1 mmol, usage of 5%) was added into the mixture,heated to 50° C. and reacted for 24 h. All the volatile components wereremoved by vacuuming at room temperature, and the remaining solid waswashed with a small amount (approximately 1.5 mL each time) n-hexane for2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.98 g(93.6%) of orange-red solid rac-MS-3k.

The composition was C₅₅H₆₀Cl₂FeSiZr(Mr=967.14): theoretical value: C,68.31; H, 6.25; measured value: C, 68.34; H, 6.27.

Synthesis Example 28 Preparation of Me[Fc(CH₂)₁₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. Fc(CH₂)₁₃CH═CH₂ (0.868 g, 2.2 mmol) (note: Fc=CpFe(C₅H₄)) andB(C₆F₅)₃ (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture,heated to 50° C. and reacted for 24 h. All the volatile components wereremoved by vacuuming at room temperature, and the remaining solid waswashed with a small amount (approximately 1.5 mL each time) n-hexane for2 to 4 times. After vacuum drying for 6 hours, 2.02 g (91.5%) oforange-red solid rac-MS-31 was obtained.

The composition was C₅₈H₆₆Cl₂FeSiZr(Mr=1009.22): theoretical value: C,69.03; H, 6.59; measured value: C, 69.04; H, 6.57.

Synthesis Example 29

The metallocene compound with R^(I) being methyl group and R^(II) beingan alkyl group can be synthesized by referring to the bridged SiH groupaddition method.

Preparation of MenBuSi(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. CH₃CH₂CH═CH₂ (0.123 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1mmol, usage of 5%) was added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Itwas dried in vacuum for 6 hours to obtain 1.12 g (76.6%) of orange-redsolid rac-MS-3m.

The composition was C₃₇H₃₆Cl₂SiZr(Mr=670.90): theoretical value: C,66.24; H, 5.41; measured value: C, 66.23; H, 5.40.

Synthesis Example 30 Preparation ofMe[n-CH₃(CH₂)₇]Si(2-Me-7-PhC₉H₄)₂ZrCl₂

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL)solvent. CH₃(CH₂)₅CH═CH₂ (0.247 g, 2.2 mmol) and B(C₆F₅)₃ (0.051 g, 0.1mmol, usage of 5%) were added into the mixture, heated to 50° C. andreacted for 24 h. All the volatile components were removed by vacuumingat room temperature, and the remaining solid was washed with a smallamount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Aftervacuum drying for 6 hours, 1.23 g (77.5%) of orange-red solid rac-MS-3nwas obtained.

The composition was C₄₁H₄₄Cl₂SiZr(Mr=727.01): theoretical value: C,67.74; H, 6.10; measured value: C, 67.72; H, 6.11.

Synthesis Example 31 Preparation of MeHSi(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂

4-phenyl-2-methylindene (2.06 g, 10 mmol) was weighed and dissolved inTol (80 ml) solvent. N-butyllithium (2.4M, 4.25 mL, 10 mmol) was slowlydropwise added into the mixture at −78° C., gradually warmed to roomtemperature and reacted overnight to obtain a wine-red solution.Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added intothe wine-red solution at −78° C., after gradually warming to roomtemperature, stirred for more than 8 hours to obtain a yellowsuspension. The yellow suspension was placed at −78° C., and lithiumtert-butylamine (0.79 g, 10 mmol) was slowly dropwise added into thesuspension, and the stirring was continued for 2 h after returning toroom temperature to obtain an orange-yellow turbid liquid. Theorange-yellow turbid liquid was placed at −78° C., and n-butyllithium(2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the liquid. Afterreturning to room temperature, stirring was continued for 2 h to obtainan orange-yellow turbid liquid. Zirconium tetrachloride (2.33 g, 10mmol) from a glove box was put into a vial, followed by adding 40 mL oftoluene, and being placed under the nitrogen protection. Zirconiumtetrachloride was added into the above yellow turbid liquid at roomtemperature, and soon the color would gradually darken fromorange-yellow to dark red. Reaction was carried out for 1 day. Thereaction solution was filtered under the protection of nitrogen, theobtained filtrate was drained of solvent, washed with n-hexane, filteredand drained to obtain a red solid. The red solid was recrystallized inmultiple steps at −20° C. from toluene to obtain the compoundMeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl₂ 2.88 g (60.0%).

The composition was C₂₁H₂₅Cl₂NSiZr(Mr=481.65): theoretical value: C,52.37; H, 5.23; N, 2.91; measured value: C, 52.40; H, 5.21; N, 2.90.

Synthesis Example 32 Preparation ofMe[Fc(CH₂)₅]Si(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂

MeHSi(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂ (0.96 g, 2 mmol) was weighed anddissolved in Tol (100 mL) solvent. Fc(CH₂)₃CH═CH₂ (0.559 g, 2.2mmol)(note: Fc=CpFe(C₅H₄)) and B(C₆F₅)₃ (0.051 g, 0.1 mmol, usage of 5%)were added into the mixture, heated to 50° C. and reacted for 24 h. Allthe volatile components were removed by vacuuming at room temperature,and the remaining solid was washed with a small amount (approximately1.5 mL each time) n-hexane for 2 to 4 times. Vacuum drying for 6 hours.A dark red solid Me[Fc(CH₂)₅]Si(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂ 1.21 g (82.1%)was obtained.

The composition was C₃₆H₄₄Cl₂FeNSiZr(Mr=736.81): theoretical value: C,58.68; H, 6.02; N, 1.90; measured value: C, 58.66; H, 6.03; N, 1.92.

B. Preparation of Metallocene Catalysts Preparation Example 1

2 g of silica gel calcined at 600° C. was weighed, and 10 mL of 10% MAOtoluene (weight percentage) was added into the silica gel, and heated to80° C. After uniformly stirring, a toluene solution of the metallocenecompound shown in formula 1 was added into the mixture, the Al/Zr ratiowas controlled to be 200:1, and the reaction was carried out overnight.The solid was collected by filtration and washed with toluene solventuntil the washed solvent was colorless, and the solid was dried undervacuum for 24 hours to obtain a solid powder, which was stored in aglove box for later use (this reaction operation method was used unlessotherwise specified). Through the measurement and calculation of thefeed amount and the metal content of the washing liquid, the catalystSC-1 with a determined metal content could be obtained, and thezirconium content was 0.268% (29.4 μmol/g).

Preparation Example 2

2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% MAO intoluene (weight percentage) and pure toluene solvent were added into themixture, heated to 80° C., stirred for 24 h and then filtered. The solidwas collected and washed with toluene solvent for 3 times. The solid wasunder vacuum drying for 24 h, and MAO-silica gel was obtained as a solidpowder.

A certain amount of MAO-silica gel was weighed, toluene solvent wasadded to form a suspension. A toluene solution of zirconocene compoundwas added into the suspension under uniform stirring, and reactedovernight. The solid was collected by filtration and washed with toluenesolvent until the washed solvent was colorless. The solid was vacuumdried for 24 hours to obtain a solid powder, which was stored in a glovebox for later use. After the feed amount and the zirconium content ofthe washing liquid were measured and calculated, a catalyst with acertain zirconium content can be obtained.

The zirconocene compound of formula 1 was selected, with controlling theAl/Zr ratio to be 50:1, 100:1, and 150:1 to prepare catalysts SC-2A(zirconium content 0.846%, 100.2 μmol/g), SC-2B (zirconium content0.430%, 47.2 μmol/g), SC-2C (zirconium content 0.282%, 32.2 μmol/g).

Preparation Example 3

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 2 was used and the Al/Zr ratiowas controlled to be 193:1, 227:1, 340:1, to obtain catalysts SC-3A(zirconium content 0.40%, 28.4 μmol/g), SC-3B (zirconium content 0.30%,25.0 μmol/g), SC-3C (zirconium content 0.20%, 16.7 μmol/g) respectively.

Preparation Example 4

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 1 was used and the Al/Zr ratiowas controlled to be 193:1, 194:1, 195:1, to obtain catalysts SC-4A(zirconium content 0.40%, 28.4 μmol/g), SC-4B (zirconium content 0.40%,28.5 μmol/g), SC-4C (zirconium content 0.40%, 28.7 μmol/g) respectively.

Preparation Example 5

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 3 was used and the Al/Zr ratiowas controlled to be 50:1, 100:1, 200:1, to obtain catalysts SC-5A(zirconium content 0.854%, 106.3 μmol/g), SC-5B(zirconium content0.441%, 49.2 μmol/g), SC-5C(zirconium content 0.277%, 30.8 μmol/g)respectively.

Preparation Example 6

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 4 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-6 (zirconium content0.453%, 51.2 μmol/g).

Preparation Example 7

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 5 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-7 (zirconium content0.441%, 48.7 μmol/g).

Preparation Example 8

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 6 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-8 (zirconium content0.437%, 50.7 μmol/g).

Preparation Example 9

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 7 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-9 (zirconium content0.463%, 52.4 μmol/g).

Preparation Example 10

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 8 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-10 (zirconiumcontent 0.425%, 47.1 μmol/g).

Preparation Example 11

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 9 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-11 (zirconiumcontent 0.439%, 48.3 μmol/g).

Preparation Example 12

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 10 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-12 (zirconiumcontent 0.482%, 52.1 μmol/g).

Preparation Example 13

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 11 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-13 (zirconiumcontent 0.501%, 54.3 μmol/g).

Preparation Example 14

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 12 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-14 (zirconiumcontent 0.410%, 44.6 μmol/g).

Preparation Example 15

2 g of silica gel calcined at 600° C. was weighed, 10 mL of 10% (weightpercentage) MAO in toluene was added into it, 0.30 g of tetrakis(pentafluorophenyl) borate dioctadecyl methyl ammonium salt was addedinto the mixture. and then 10 mL of toluene was added into the mixture,and heated to 80° C., stirred for 24 h. The resulting mixture wasfiltered, and the solid was collected and washed with toluene solventfor 3 times. The solid was vacuum dried for 24 h to obtain 3.1 g ofsolid powdered carrier silica gel.

2 g of the treated carrier silica gel was weighed and 20 mL of toluenesolvent was added into the carrier silica gel to form a suspension. 5 mLof toluene solution prepared by adding 100 mg of the zirconocenecompound shown in Formula 12 was added into the suspension underuniformly stirring, and stirred at room temperature overnight. The solidwas collected by filtration and washed with toluene solvent until thewashed solvent was colorless. The solid was vacuum dried for 24 hours toobtain a solid catalyst powder (SC-15) with a Zr content of 0.390% bymass (42.39 μmol/g), which was stored in a glove box for later use.

Preparation Example 16

The only difference from Preparation Example 15 is thattris(pentafluorophenyl)borane of the same quality was used to replacetetrakis(pentafluorophenyl)borate dioctadecylmethylammonium salt andother conditions remained unchanged to obtain a solid catalyst 3.2 g,which has a tested zirconium content of 0.45% by mass.

Preparation Example 17

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 13 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-16 (zirconiumcontent 0.406%, 43.7 μmol/g).

Preparation Example 18

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 14 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-17 (zirconiumcontent 0.415%, 45.9 μmol/g).

Preparation Example 19

Preparation steps were the same as those in Preparation Example 2. Themetallocene compound as shown in formula 15 was used and the Al/Zr ratiowas controlled to be 100:1, to obtain a catalyst SC-18 (zirconiumcontent 0.371%, 40.2 μmol/g).

Preparation Example 20

Some of the metallocene compounds in Synthesis Examples 2-18 were takento prepare catalysts for olefin polymerization. The preparation processwas as follows:

2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% (weightpercentage) MAO in toluene and pure toluene solvent 40-100 mL was addedin it, heated to 80° C., and stirred for 24 h. The resulting mixture wasfiltered, and the solid was collected and washed with toluene solventfor three times. Next, the solid was dried under vacuum for 24 hours toobtain a solid powder of MAO-silica gel.

A certain amount of MAO-silica gel was weighed, toluene solvent wasadded into it to form a suspension. A part of the toluene solution ofthe zirconocene compound of the examples was added into the suspensionunder uniformly stirring, and reacted overnight. The solid was collectedby filtration and washed with toluene solvent until the washed solventwas colorless, and the solid was vacuum dried for 24 hours to obtain asolid powder, which was stored in a glove box for later use. After thefeed amount and the zirconium content of the washing liquid weremeasured and calculated, a catalyst with a certain zirconium contentcould be obtained.

Among them:

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundrac-MS-1b was taken, to obtain a catalyst rac-MS-1b-C, wherein zirconiumcontent was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 50:1 and zirconocene compound rac-MS-1jwas taken, to obtain a catalyst rac-MS-1j-C, wherein zirconium contentwas 0.846% (100.2 μmol/g).

Al/Zr ratio was controlled to be 100:1 and zirconocene compoundrac-MS-3a was taken, to obtain a catalyst rac-MS-3a-C, wherein zirconiumcontent was 0.430% (47.2 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundrac-MS-3b was taken, to obtain a catalyst rac-MS-3b-C, wherein zirconiumcontent was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundrac-MS-4a was taken, to obtain a catalyst rac-MS-4a-C, wherein zirconiumcontent was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundrac-MS-4b was taken, to obtain a catalyst rac-MS-4b-C, wherein zirconiumcontent was 0.268% (29.4 μmol/g).

Preparation Example 21

The metallocene compounds prepared in Synthesis Examples 19-32 were usedto prepare the catalyst for olefin polymerization. The preparationprocess was as follows:

2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% (weightpercentage) MAO in toluene and pure toluene solvent 40-100 mL was addedinto it, heated to 80° C. and stirred for 24 h. The resulting mixturewas filtered, and the solid was collected and washed with toluenesolvent three times. Next, the solid was dried under vacuum for 24 hoursto obtain a solid powder of MAO-silica gel.

A certain amount of MAO-silica gel was weighed, toluene solvent wasadded to form a suspension. A part of the toluene solution of thezirconocene compound of the examples was added into the mixture underuniformly stirring, and react overnight. The solid was collected byfiltration and washed with toluene solvent until the washed solvent wascolorless, and the solid was vacuum dried for 24 hours to obtain a solidpowder, which was stored in a glove box for later use. After the feedamount and the zirconium content of the washing liquid were measured andcalculated, a catalyst with a certain zirconium content could beobtained.

Among them:

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[(PhMeN(CH₂)₅)]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3c-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[PhMeN(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrC₂ was taken, to obtain a catalystrac-MS-3d-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[PhMeN(CH₂)₁₂]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3e-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[PhMeN(CH₂)₁₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3f-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[p-ClC₆H₄MeN(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain acatalyst rac-MS-3 g-C, wherein zirconium content was 0.268% (29.4μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[p-MeOC₆H₄MeN(CH₂)₅]Si(2-Me-7-PhC₉H₄) ZrCl₂ was taken, to obtain acatalyst rac-MS-3h-C, wherein zirconium content was 0.268% (29.4μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[Fc(CH₂)₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3i, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe(Fc(CH₂)₅)Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3j, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[Fc(CH₂)₁₂]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3k-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[Fc(CH₂)₁₅]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3l, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMenBuSi(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3m-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[n-CH₃(CH₂);]Si(2-Me-7-PhC₉H₄)₂ZrCl₂ was taken, to obtain a catalystrac-MS-3n-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and compoundMeHSi(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂ was taken, to obtain a catalystrac-MS-3o-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compoundMe[Fc(CH₂)₅]Si(4-Ph-2-MeC₉H₄)(NtBu)ZrCl₂ was taken, to obtain a catalystrac-MS-3p-C, wherein zirconium content was 0.268% (29.4 μmol/g).

C. Catalytic Reaction Example 1

A 300 mL autoclave was selected, vacuumed in an oil bath at 100° C., andreplaced with nitrogen for 3 times before use.

The pressurized catalyst adding device was dried and transferred into aglove box, added a measured amount of catalyst, and added a small amountof solvent to mix well. The device was took out from the glove box, andattached to the autoclave device to start the polymerization experiment.

The polymerization experiment conditions are as follows: setting acertain temperature, pressure and reaction time. Taking into account theindustrial production and application, the polymerization experimentsthat have been completed gave priority to the choice of co-catalysts,that is, avoiding or minimizing the use of expensive MAO, and switchingto using cheaper alkyl aluminum reagents. (If there was no specialinstructions below, this reaction method was used.)

200 mg of SC-1 catalyst was used, without using solvent, the reactiontime was 30 minutes, the reaction temperature was 80° C., and 50 g ofpropylene was pressed into the device.

Finally, 23.5 g of polymer was obtained, and the calculated activity was2.35×10⁶ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 2

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

105 mg of SC-2A catalyst and 8 mL of triisobutyl aluminum (concentrationof 150 μmol/mL, aluminum-zirconium ratio of about 500:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., andthe pressure of propylene >3.9 MPa.

Finally, 92 g of polymer was obtained, and the calculated polymerizationactivity was 4.00×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was 131324, the Mw was325745, and the PDI value was 2.48, all of them were measured by thehigh temperature GPC; the isotacticity measured by the high temperature¹³C NMR spectrum was [mmmm] 99.4%. The melting point test value was151.33° C. (Note: PP analysis was selective.)

Example 3

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

105 mg of SC-2B catalyst and 3.2 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., and the pressure of propylene >3.9 MPa.

Finally, 64 g of polymer was obtained, and the calculated polymerizationactivity was 2.78×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 4

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

106 mg of SC-2C catalyst, triisobutyl aluminum 3.2 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., andthe pressure of propylene >3.9 MPa.

Finally, 57 g of polymer was obtained, and the calculated polymerizationactivity was 2.45×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 5

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

105 mg of SC-3A catalyst and 8 mL of triisobutyl aluminum (concentrationof 150 μmol/mL, aluminum-zirconium ratio of about 500:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., andthe pressure of propylene >3.9 MPa.

Finally, 80 g of polymer was obtained, and the calculated polymerizationactivity was 3.48×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was 133064, the Mw was313745, and the PDI value was 2.36, all of them were measured by thehigh temperature GPC; and the isotacticity measured by the hightemperature ¹³C NMR spectrum was [mmmm] 99.3%. The melting point testvalue was 149.43° C.

Example 6

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

105 mg of SC-3B catalyst and 3.2 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., and the pressure of propylene >3.9 MPa.

Finally, 52 g of polymer was obtained, and the calculated polymerizationactivity was 2.26×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 7

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-3C catalyst 106 mg and triisobutyl aluminum 3.2 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., andthe pressure of propylene >3.9 MPa.

Finally, 43 g of polymer was obtained, and the calculated polymerizationactivity was 1.85×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 8

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

98 mg of SC-4A catalyst and 15 mL of triisobutyl aluminum (concentrationof 150 mol/mL, aluminum-zirconium ratio of about 549:1) were used, thereaction time was 240 minutes, the reaction temperature was 75° C., andthe amount of propylene was 528.7 g.

Finally, 450 g of polymer was obtained, and the calculatedpolymerization activity was 1.098×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹. Mn was162913, Mw was 377577, and PDI value was 2.317, all of them weremeasured by the high temperature GPC; the isotacticity measured by hightemperature ¹³C NMR spectrum was [mmmm] 99.6%. The melting point testvalue was 151.4° C.

Example 9

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 60 mg and triisobutyl aluminum 15 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 896:1 amount) were used,the reaction time was 330 minutes, the reaction temperature was 75° C.,and the amount of propylene was 518 g.

Finally, 860 g of polymer was obtained, and the calculatedpolymerization activity was 1.772×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was104205, the Mw was 226218, and the PDI value was 2.17, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 98.4%. The melting pointtest value was 152.2/161.4° C.

Example 10

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 60 mg and triethylaluminum 3 mL (concentration of 100μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene 538 g, and the amount of hydrogen was 0.02 g.

Finally, 80 g of polymer was obtained, and the calculated polymerizationactivity was 3.186×10⁷ g(PP)·mol(Zr)·h⁻¹.

Example 11

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of SC-4A catalyst and 2.5 mL of triethylaluminum (concentration of100 μmol/mL, aluminum-zirconium ratio of about 1707:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

Finally, 35 g of polymer was obtained, and the calculated polymerizationactivity was 2.389×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 12

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 65 mg and triisobutyl aluminum 20 mL (concentration of150 μmol/mL, and aluminum zirconium ratio of about 1792:1 amount) wereused, the reaction time was 270 minutes, the reaction temperature was75° C., the amount of propylene was 659 g, the amount of hydrogen was0.026 g.

Finally, 600 g of polymer was obtained, and the calculatedpolymerization activity was 2.206×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was80551, the Mw was 188015, and the PDI value was 2.33, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.7%. The melting pointtest value was 151.83/152.2° C.

Example 13

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

40 mg SC-4A catalyst and triisobutyl aluminum 20 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1707:1 volume) were used,the reaction time was 180 minutes, the reaction temperature was 75° C.,the amount of propylene was 628.6 g, and the amount of hydrogen was1.365 g.

Finally, 270 g of polymer was obtained, and the calculatedpolymerization activity was 1.613×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 14

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 30 mg, triisobutyl aluminum 20 mL (concentration of 150μmol/mL, aluminum-zirconium ratio of about 2389:1 volume) were used, thereaction time was 360 minutes, the reaction temperature was 75° C., theamount of propylene was 658.8 g, and the amount of hydrogen was 0.052 g.

Finally, 390 g of polymer was obtained, and the calculatedpolymerization activity was 3.106×10⁸ g(PP)·mol(Zr)·h⁻¹. Mn was 47736,Mw was 146937, and PDI value was 3.08, all of them were measured by thehigh temperature GPC.

Example 15

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 30 mg and triisobutyl aluminum 20 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 2389:1 volume) were used,the reaction time was 180 minutes, the reaction temperature was 75° C.,the amount of propylene is 357.2 g, and the amount of hydrogen was 0.06g.

Finally, 205 g of polymer was obtained, and the calculatedpolymerization activity was 1.633×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹. The meltingpoint test value was 154.03° C.

Example 16

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 30 mg, triisobutyl aluminum 10 mL (concentration of 150μmol/mL, aluminum-zirconium ratio of about 1195.1) were used, thereaction time was 420 minutes, the reaction temperature was 75° C., theamount of propylene was 682 g, and the amount of hydrogen was 0.06 g.

Finally, 540 g of polymer was obtained, and the calculatedpolymerization activity was 4.301×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 17

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 20 mg and triisobutyl aluminum 3.5 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 627:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 657 g, and the amount of hydrogen was 0.06 g.

Finally, 10 g of polymer was obtained, and the calculated polymerizationactivity was 1.195×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 18

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 20 mg and triisobutyl aluminum 7 mL (concentration of 150μmol/mL, aluminum-zirconium ratio of about 1254:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 651 g, and the amount of hydrogen was 0.06 g.

Finally, 45 g of polymer was obtained, and the calculated polymerizationactivity was 5.376×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 19

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 20 mg, triisobutyl aluminum 10 mL (concentration of 150μl mol/mL, aluminum-zirconium ratio of about 1792:1 amount), thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 654 g, the amount of hydrogen was 0.06 g.

Finally, 82 g of polymer was obtained, and the calculated polymerizationactivity was 9.797×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 20

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 20 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1792:1 amount) were used,the reaction time was 180 minutes, the reaction temperature was 75° C.,the amount of propylene was 652 g, and the amount of hydrogen was 0.06g.

Finally, 92 g of polymer was obtained, and the calculated polymerizationactivity was 1.099×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 21

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4A catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1195:1 volume) were used,the reaction time was 420 minutes, the reaction temperature was 75° C.,the amount of propylene was 670 g, and the amount of hydrogen was 0.06g.

Finally, 530 g of polymer was obtained, and the calculatedpolymerization activity was 4.221×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 22

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 480 minutes, the reaction temperature was 75° C., theamount of propylene was 684 g, and the amount of hydrogen was 0.06 g.

Finally, 610 g of polymer was obtained, and the calculatedpolymerization activity was 4.859×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 23

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 240 minutes, reaction temperature was 75° C., theamount of propylene was 687.5 g, and the amount of hydrogen was 0.06 g.

Finally, 533 g of polymer was obtained, and the calculatedpolymerization activity was 4.245×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹. The meltingpoint test value was 155.46° C.

Example 24

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 240 minutes, the reaction temperature was 75° C., theamount of propylene was 688.6 g, and the amount of hydrogen was 0.06 g.

Finally, 405 g of polymer was obtained, and the calculatedpolymerization activity was 3.226×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 25

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4C catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 680 g, and the amount of hydrogen was 0.06 g.

Finally, 530 g of polymer was obtained, and the calculatedpolymerization activity was 4.221×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 26

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-4C catalyst 20 mg and triisobutyl aluminum 10 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 1792:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 681 g, and the amount of hydrogen was 0.06 g.

Finally, 145 g of polymer was obtained, and the calculatedpolymerization activity was 1.732×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 27

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

98 mg of SC-5A catalyst and 15 mL of triisobutyl aluminum (concentrationof 150 μmol/mL, aluminum to zirconium ratio of about 549:1 amount) wereused, the reaction time was 240 minutes, the reaction temperature was75° C., and the amount of propylene amount was 523 g.

Finally, 461 g of polymer was obtained, and the calculatedpolymerization activity was 1.106×10⁷ g(PP)·mol⁻¹(Zr)·h. The Mn was174912, the Mw was 366583, and the PDI value was 2.09, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 98.4%. The melting pointtest value was 153.1° C.

Example 28

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-5B catalyst 60 mg and triisobutyl aluminum 15 mL (concentration of150 μmol/mL, aluminum-zirconium ratio of about 896:1 amount) were used,the reaction time was 330 minutes, the reaction temperature was 75° C.,and the amount of propylene was 521 g.

Finally, 451 g of polymer was obtained, and the calculatedpolymerization activity was 2.788×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was115708, the Mw was 236654, and the PDI value was 2.045, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.1%. The melting pointtest value was 154.9° C.

Example 29

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

SC-5C catalyst 60 mg and triethylaluminum 3 mL (concentration 100μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, thereaction time was 180 minutes, the reaction temperature was 75° C., theamount of propylene was 534 g, and the amount of hydrogen was 0.02 g.

Finally, 91 g of polymer was obtained, and the calculated polymerizationactivity was 1.641×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 30

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

98 mg of SC-6 catalyst and 15 mL of triisobutyl aluminum (concentrationof 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, thereaction time was 240 minutes, the reaction temperature was 75° C., andthe amount of propylene was 541 g.

Finally, 424 g of polymer was obtained, and the calculatedpolymerization activity was 2.112×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. Mn was168742, Mw was 368213, and PDI value was 2.18, all of them were measuredby the high temperature GPC; the isotacticity measured by hightemperature ¹³C NMR spectrum was [mmmm] 98.9%. The melting point testvalue was 155.4° C.

Example 31

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-7 catalyst and 15 mL of triisobutyl aluminum (concentrationof 150 mol/mL, aluminum-zirconium ratio of about 549:1) were used, thereaction time was 240 minutes, the reaction temperature was 75° C., andthe amount of propylene was 539 g.

Finally, 447 g of polymer was obtained, and the calculatedpolymerization activity was 2.294×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was19,863, the Mw was 398423, and the PDI value was 2.01, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.2%. The melting pointtest value was 157.1° C.

Example 32

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-8 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene amount was 534 g.

Finally, 451 g of polymer was obtained, and the calculatedpolymerization activity was 2.223×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was215821, the Mw was 439429, and the PDI value was 2.036, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.4%. The melting pointtest value was 159.1° C.

Example 33

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-9 catalyst and 15 mL of triisobutyl aluminum (concentrationof 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, thereaction time was 240 minutes, the reaction temperature was 75° C., andthe amount of propylene was 544 g.

Finally, 472 g of polymer was obtained, and the calculatedpolymerization activity was 2.252×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was175941, the Mw was 419745, and the PDI value was 2.386, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.5%. The melting pointtest value was 161.4° C.

Example 34

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-10 catalyst and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene was 521 g.

Finally, 469 g of polymer was obtained, and the calculatedpolymerization activity was 2.489×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was155967, the Mw was 430741, and the PDI value was 2.762, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 97.2%. The melting pointtest value was 147.9° C.

Example 35

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-11 catalyst and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene was 521 g.

Finally, 471 g of polymer was obtained, and the calculatedpolymerization activity was 2.437×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was152134, the Mw was 416572, and the PDI value was 2.738, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature 13C NMR spectrum was [mmmm] 97.5%. The melting pointtest value was 148.1° C.

Example 36

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-12 catalyst and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene was 529 g.

Finally, 487 g of polymer was obtained, and the calculatedpolymerization activity was 2.336×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was142879, the Mw was 396654, and the PDI value was 2.776, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 96.6%. The melting pointtest value was 144.7° C.

Example 37

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-13 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene was 542 g.

Finally, 469 g of polymer was obtained, and the calculatedpolymerization activity was 2.159×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was162678, the Mw was 396789, and the PDI value was 2.439, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 97.6%. The melting pointtest value was 152.9° C.

Example 38

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-14 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL) were used, the reaction time was 240minutes, the reaction temperature was 75° C., and the amount ofpropylene was 582 g.

Finally, 459 g of polymer was obtained, and the calculatedpolymerization activity was 2.573×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. Mn was182668, Mw was 406769, and PDI value was 2.226, all of them weremeasured by the high temperature GPC; the isotacticity measured by hightemperature ¹³C NMR spectrum was [mmmm] 95.6%. The melting point testvalue was 147.9° C.

Example 39

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-15 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL) were used, the reaction time was 240minutes, the reaction temperature was 75° C., and the amount ofpropylene was 552 g.

Finally, 485 g of polymer was obtained. The PDI value measured by hightemperature GPC was 2.028; the isotacticity measured by high temperature¹³C NMR spectrum was [mmmm] 96.3%. The melting point test value was148.5° C.

Example 40

The evaluation conditions were the same as in Example 39, and thecatalyst prepared in Example 16 was used. 560 g of propylene was usedand 300 g of polypropylene powder was obtained. The PDI measured by GPCwas 2.678, and the isotacticity measured by the high temperature ¹³C NMRspectrum was [mmmm] 92.6%. The melting point test value was 145.1° C.

Example 41

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-16 catalyst and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL) were used, the reaction time was 240minutes, the reaction temperature was 75° C., and the amount ofpropylene was 582 g.

Finally, 418 g of polymer was obtained, and the calculatedpolymerization activity was 2.434×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was172761, the Mw was 435432, and the PDI value was 2.520, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 96.7%. The melting pointtest value was 148.8° C.

Example 42

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-17 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL) were used, the reaction time was 240minutes, the reaction temperature was 75° C., and the amount ofpropylene was 582 g.

Finally, 401 g of polymer was obtained, and the calculatedpolymerization activity was 2.248×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was123758, the Mw was 467327, and the PDI value was 3.776, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 92.4%. The tested meltingpoint was 140.2° C.

Example 43

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

100 mg of SC-18 catalyst, and 15 mL of triisobutyl aluminum(concentration of 150 μmol/mL) were used, the reaction time was 240minutes, the reaction temperature was 75° C., and the amount ofpropylene was 582 g.

Finally, 491 g of polymer was obtained, and the calculatedpolymerization activity was 2.752×10⁷ g(PP) mol⁻¹(Zr)·h⁻¹. The Mn was186469, the Mw was 404219, and the PDI value was 2.168, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 97.2%. The melting pointtest value was 148.7° C.

Example 44

A 300 mL autoclave was used for the polymerization reaction (300 mLreactor was used in the following examples unless otherwise specified),vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3times before use.

The pressurized catalyst adding device was dried and transferred into aglove box, added a measured amount of catalyst, and added a small amountof solvent to mix well. The device was took out from the glove box, andattached to the autoclave device to start the polymerization experiment.

The polymerization experiment conditions are as follows: setting acertain temperature, pressure and reaction time. Taking into account theindustrial production and application, the polymerization experimentsthat have been completed gave priority to the choice of co-catalysts,that is, avoiding or minimizing the use of expensive MAO, and switchingto using cheaper alkyl aluminum reagents.

50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200)were used, the reaction time was 60 minutes, the reaction temperaturewas 50° C., and the ethylene pressure in the autoclave was 1 MPa.

Finally, 10 g of polymer was obtained, and the calculated polymerizationactivity was 6.8×10⁶ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 45

The polymerization conditions were basically the same as in Example 44,except that 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutylaluminum (concentration of 150 μmol/mL, aluminum/zirconium ratio ofabout 200), the reaction time was 60 minutes, the reaction temperaturewas 50° C., and the ethylene pressure was 2 MPa.

Finally, 16 g of polymer was obtained, and the calculated polymerizationactivity was 1.08×10⁷ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 46

The polymerization conditions were basically the same as those inExample 44, except that 150 mg of rac-MS-1b-C catalyst and 0.2 mL of MAO(10% by mass in Tol, aluminum/zirconium ratio of about 200:1) were used,the reaction time was 60 minutes, the reaction temperature was 50° C.,and the ethylene pressure was 1 MPa.

Finally, 35 g of polymer was obtained, and the calculated polymerizationactivity was 6.99′10⁶ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 47

The polymerization conditions were basically the same as those inExample 44, except that: 113 mg of rac-MS-1j-C catalyst and 15 mL oftriisobutyl aluminum solution (concentration of 150 μmol/mL,aluminum/zirconium ratio of about 200:1) were used, the reaction timewas 60 minutes, the reaction temperature was 50° C., and the ethylenepressure was 1 MPa.

Finally, 10 g of polymer was obtained, and the calculated polymerizationactivity was 0.88×10⁶ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 48

The polymerization conditions were basically the same as those inExample 44, except that: 150 mg of rac-MS-3a-C catalyst and 6.3 mL oftriisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconiumratio of about 200:1) were used, the reaction time was 60 minutes, thereaction temperature was 50° C., and the ethylene pressure was 1 MPa.

Finally, 21 g of polymer was obtained, and the calculated polymerizationactivity was 4.45×10⁶ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 49

The polymerization conditions were basically the same as those inExample 44, except that 150 mg of rac-MS-3b-C catalyst and 1.75 mL oftriisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconiumratio of about 200:1) were used, the reaction time was 60 minutes, thereaction temperature was 50° C., and the ethylene pressure was 1 MPa.

Finally, 36 g of polymer was obtained, and the calculated polymerizationactivity was 2.74×10⁷ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 50

The polymerization conditions were basically the same as those inExample 44, except that 150 mg of rac-MS-4a-C catalyst and 6.3 mL oftriisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconiumratio of about 200:1) were used, the reaction time was 60 minutes, thereaction temperature was 50° C., and the ethylene pressure was 1 MPa.

Finally, 54 g of polymer was obtained, and the calculated polymerizationactivity was 1.22×10⁷ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 51

The polymerization conditions were basically the same as those inExample 44, except that 150 mg of rac-MS-4b-C catalyst and 3.75 mL oftriisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconiumratio of about 200:1) were used, the reaction time was 60 minutes, thereaction temperature was 50° C., and the ethylene pressure was 2 MPa.

Finally, 62 g of polymer was obtained, and the calculated polymerizationactivity was 1.41×10⁷ g(PE)·mol⁻¹(Zr)·h⁻¹.

Example 52

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

112 mg of rac-MS-1b-C catalyst and 8 mL of triisobutyl aluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 500:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the propylene pressure>3.9 MPa.

Finally, 91 g of the polymer was obtained, and the calculatedpolymerization activity was 9.20×10⁶ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was133945, the Mw was 342375, and the PDI value was 2.57, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.3%. The melting pointtest value was 157.63° C.

Example 53

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

101 mg of rac-MS-1j-C catalyst and 3.2 mL of triisobutylaluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., and the propylene pressure >3.9 MPa.

Finally, 132 g of polymer was obtained, and the calculatedpolymerization activity was 4.33×10⁶ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was127361, the Mw was 36.431, and the PDI value was 2.83, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 98.6%. The melting pointtest value was 152.3° C.

Example 54

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

104 mg of rac-MS-1b-C catalyst and 15 mL of triisobutylaluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., and the amount of propylene was 528.7 g.

Finally, 412 g of polymer was obtained, and the calculatedpolymerization activity was 3.37×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was173453, the Mw was 394257, and the PDI value was 2.273, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 99.1%. The melting pointtest value was 154.4° C.

Example 55

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

104 mg of rac-MS-1b-C catalyst and 15 mL of triethylaluminum(concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1)were used, the reaction time was 240 minutes, the reaction temperaturewas 75° C., the amount of propylene was 538 g, and the amount ofhydrogen was 0.02 g.

Finally, 478 g of polymer was obtained, and the calculatedpolymerization activity was 1.54×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was135427, the Mw was 397892, and the PDI value was 2.938, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 98.4%. The melting pointtest value was 153.2° C.

Example 56

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-1j-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1707:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 135 g of polymer was obtained, and the calculatedpolymerization activity was 4.37×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹. The Mn was82451, the Mw was 213509, and the PDI value was 2.59, all of them weremeasured by the high temperature GPC; the isotacticity measured by thehigh temperature ¹³C NMR spectrum was [mmmm] 96.7%. The melting pointtest value was 147.83/150.2° C.

Example 57

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3c-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 469 g of polymer was obtained, and the calculatedpolymerization activity was 1.52×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 58

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3d-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 455 g of polymer was obtained, and the calculatedpolymerization activity was 1.47×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 59

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3e-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 492 g of polymer was obtained, and the calculatedpolymerization activity was 1.59×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 60

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3f-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 421 g of polymer was obtained, and the calculatedpolymerization activity was 1.36×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 61

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3 g-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about1200:1), the reaction time was 180 minutes, the reaction temperature was75° C., the amount of propylene is 512 g, and the amount of hydrogen was0.02 g.

Finally, 387 g of polymer was obtained, and the calculatedpolymerization activity was 1.25×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 62

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3h-C catalyst, 2.5 mL of triethylaluminum (concentrationof 100 μmol/mL, the ratio of aluminum to zirconium was about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene is 512 g, and the amount of hydrogenwas 0.02 g.

Finally, 418 g of polymer was obtained, and the calculatedpolymerization activity was 1.35×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 63

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3i-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 441 g of polymer was obtained, and the calculatedpolymerization activity was 1.43×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 64

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3j-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 427 g of polymer was obtained, and the calculatedpolymerization activity was 1.38×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 65

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3k-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 434 g of polymer was obtained, and the calculatedpolymerization activity was 1.41×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 66

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3l-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 395 g of polymer was obtained, and the calculatedpolymerization activity was 1.27×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Example 67

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3p-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 352 g of polymer was obtained, and the calculatedpolymerization activity was 1.14′10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Comparative Example 1

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3m-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about1200:1), the reaction time was 180 minutes, the reaction temperature was75° C., the amount of propylene was 512 g, and the amount of hydrogenwas 0.02 g.

Finally, 425 g of polymer was obtained, and the calculatedpolymerization activity was 1.38×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Comparative Example 2

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3n-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 420 g of polymer was obtained, and the calculatedpolymerization activity was 1.36×10⁸ g(PP)·mol⁻¹(Zr)·h⁻¹.

Comparative Example 3

A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C.,and replaced with nitrogen for 3 times before use.

35 mg of rac-MS-3o-C catalyst and 2.5 mL of triethylaluminum(concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1)were used, the reaction time was 180 minutes, the reaction temperaturewas 75° C., the amount of propylene was 512 g, and the amount ofhydrogen was 0.02 g.

Finally, 268 g of polymer was obtained, and the calculatedpolymerization activity was 8.68×10⁷ g(PP)·mol⁻¹(Zr)·h⁻¹.

For easy comparison and analysis, the above experimental data aresummarized in the following tables.

TABLE 1 Polymerization product properties Catalyst Reaction MeltingAl/Zr Al/Zr Metallocene compound Catalyst Isotacticity point ItemCatalyst ratio ratio R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) Activity Mn MwPDIvvalue (%) (° C.) Example SC-1 200:1 — Me PhMeNH₂CH₂CH₂C(4-Ph-2-MeC₉H₄)₂ 2.35 — — — — — 1 Example SC-2A  50:1  500:1 MePhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 40 131324 325745 2.48 99.4 151.33 2Example SC-2B 100:1  200:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 27.8 — — —— — 3 Example SC-2C 150:1  200:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 24.5— — — — — 4 Example SC-3A 193:1  500:1 Me PhMeNH₂CH₂CH₂CH₂C(4-Ph-2-MeC₉H₄)₂ 34.8 133064 313745 2.36 99.3 149.43 5 Example SC-3B227:1  200:1 Me PhMeNH₂CH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 22.6 — — — — — 6Example SC-3C 340:1  200:1 Me PhMeNH₂CH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 18.5 —— — — — 7 Example SC-4A 193:1  549:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂109.8 162913 377577 2.317 99.6 151.4 8 Example SC-4A 193:1  896:1 MePhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 177.2 104205 226218 2.17 98.4 161.4 9Example SC-4A 193:1 1195:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 31.86 — —— — — 10 Example SC-4A 193:1 1707:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂23.89 — — — — — 11 Example SC-4A 193:1 1792:1 Me PhMeNH₂CH₂CH₂C(4-Ph-2-MeC₉H₄)₂ 220.6 80551 188015 2.33 99.7 152.2 12 Example SC-4A193:1 1707:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 161.3 — — — — — 13Example SC-4A 193:1 2389:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 310.647736 146937 3.08 — — 14 Example SC-4A 193:1 2389:1 Me PhMeNH₂CH₂CH₂C(4-Ph-2-MeC₉H₄)₂ 163.3 — — — — 154.03 15 Example SC-4A 193:1 1195:1 MePhMeNH₂CH₂CH₂C (4-Ph-2-MeC₉H₄)₂ 430.1 — — — — — 16

TABLE 2 Polymerization product properties Catalyst Reaction MeltingAl/Zr Al/Zr Metallocene compound Catalyst PD Isotacticity point ItemCatalyst ratio ratio R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) activity Mn Mwvalue (%) (° C.) Example SC-4A 193:1  627:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-11.95 — — — — — 17 MeC₉H₄)₂ Example SC-4A 193:1 1254:1 Me PhMeNH₂CH₂CH₂C(4-Ph-2- 53.76 — — — — — 18 MeC₉H₄)₂ Example SC-4A 193:1 1792:1 MePhMeNH₂CH₂CH₂C (4-Ph-2- 97.97 — — — — — 19 MeC₉H₄)₂ Example SC-4A 193:11792:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2- 109.9 — — — — — 20 MeC₉H₄)₂ ExampleSC-4A 193:1 1195:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2- 422.1 — — — — — 21MeC₉H₄)₂ Example SC-4B 194:1 1195:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2- 485.9 — —— — — 22 MeC₉H₄)₂ Example SC-4B 194:1 1195:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2-424.5 — — — — 155.46 23 MeC₉H₄)₂ Example SC-4B 194:1 1195:1 MePhMeNH₂CH₂CH₂C (4-Ph-2- 322.6 — — — — — 24 MeC₉H₄)₂ Example SC-4C 195:11195:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2- 422.1 — — — — — 25 MeC₉H₄)₂ ExampleSC-4C 195:1 1792:1 Me PhMeNH₂CH₂CH₂C (4-Ph-2- 173.2 — — — — — 26MeC₉H₄)₂ Example SC-5A  50:1  549:1 Me Me₂NH₂CH₂CH₂CH₂C (4-Ph-2- 11.06174912 366583 2.09 98.4 153.1 27 MeC₉H₄)₂ Example SC-5B 100:1  896:1 MeMe₂NH₂CH₂CH₂CH₂C (4-Ph-2- 27.88 115708 236654 2.045 99.1 154.9 28MeC₉H₄)₂ Example SC-5C 200:1 1195:1 Me Me₂NH₂CH₂CH₂CH₂C (4-Ph-2- 16.41 —— — — — 29 MeC₉H₄)₂ Example SC-6 100:1  549:1 Me Me₂NH₂CH₂C (4-Ph-2-21.12 168742 368213 2.18 98.9 155.4 30 MeC₉H₄)₂ Example SC-7 100:1 549:1 Me (Me₂NH₂CH₂CH₂C (4-Ph-2- 22.94 198563 398423 2.01 99.2 157.1 31MeC₉H₄)₂ Example SC-8 100:1  549:1 Me NH₂Pr₂NH₂CH₂CH₂C (4-Ph-2- 22.23215821 439429 2.036 99.4 159.1 32 MeC₉H₄)₂

TABLE 3 Polymerization product properties Catalyst Reaction Isotac-Melting Al/Zr Al/Zr Metallocene compound Catalyst PDI ticity point ItemCatalyst ratio ratio R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) activity Mn Mwvalue (%) (° C.) Example SC-9 100:1 549:1 Me iPr₂NH₂CH₂CH₂C (4-Ph-2-22.52 175941 419745 2.386 99.5 161.4 33 MeC₉H₄)₂ Example SC-10 100:1549:1 Me iBuMeNH₂CH₂CH₂C (4-Ph-2- 24.89 155967 430741 2.762 97.2 147.934 MeC₉H₄)₂ Example SC-11 100:1 549:1 Me iBuEtNH₂CH₂CH₂C (4-Ph-2- 24.37152134 416572 2.738 97.5 148.1 35 MeC₉H₄)₂ Example SC-12 100:1 549:1 MeiPrEtNH₂CH₂CH₂C (4-Ph-2- 23.36 142879 396654 2.776 96.6 144.7 36MeC₉H₄)₂ Example SC-13 100:1 549:1 Me₂NH₂CH₂C iBuMeNH₂CH₂CH₂C (4-Ph-2-21.59 162678 396789 2.439 97.6 152.9 37 MeC₉H₄)₂ Example SC-14 100:1 —Me FcCH₂CH₂ (4-Ph-2- 25.73 182668 406769 2.226 95.6 147.9 38 MeC₉H₄)₂Example SC-15 — — Me FcCH₂CH₂ (4-Ph-2- — — — 2.028 96.3 148.5 39MeC₉H₄)₂ Example Prep- — — Me FcCH₂CH₂ (4-Ph-2- — — — 2.678 92.6 145.140 aration MeC₉H₄)₂ Exam- ple 16 Example SC-16 100:1 — Me FcCH₂CH₂CH₂(4-Ph-2- 24.34 172761 435432 2.520 96.7 148.8 41 MeC₉H₄)₂ Example SC-17100:1 — Me FcCH₂ (4-Ph-2- 22.48 123758 467327 3.776 92.4 140.2 42MeC₉H₄)₂ Example SC-18 100:1 — Me FcCH₂CH₂ (4-(4- 27.52 186469 4042192.168 97.2 148.7 43 tBuC₆H₄)-2- MeC₉H₄)₂ Note: In Tables 1-3, the unitof catalyst activity in Examples 1-43 is 10⁶ g(PP) · mol − 1(Zr) · h⁻¹.″—″means there is no such data. According to the data in Tables 1-3:1)When the substituents on the bridging atoms in the metallocenecompound include amine-substituted C₂-C₄ groups ormetallocene-substituted C₁-C₃ groups, the prepared catalyst has highercatalytic activity for the polymerization of propylene and obtainedpolymerization products with suitable molecular weights, PDI values,isotacticity and melting points. 2)By adjusting the types ofsubstituents on the bridging atoms in the metallocene compound,polymerization products with different molecular weights and differentmelting points can be obtained. 3)The polymerization activity of thecatalyst can be further optimized by adjusting the test conditions suchas Al/Zr ratio of the catalyst and/or the Al/Zr ratio of thepolymerization system, as illustrated by Examples 1-4, and Examples8-11.

TABLE 4 Catalyst Reaction Metallocene Compound Catalyst Item CatalystAl/Zr ratio Al/Zr ratio R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) activityExample rac-MS-1b-C 200:1 200:1 Me PhMeNCH₂CH₂ (2-Me-7-p-tBuC₆H₄C₉H₄)₂6.8 44 Example rac-MS-1b-C 200:1 200:1 Me PhMeNCH₂CH₂(2-Me-7-p-tBuC₆H₄C₉H₄)₂ 10.8 45 Example rac-MS-1b-C 200:1 200:1 MePhMeNCH₂CH₂ (2-Me-7-p-tBuC₆H₄C₉H₄)₂ 6.99 46 Example rac-MS-1j-C  50:1200:1 Me FcCH₂CH₂ (2-Me-7-p-tBuC₆H₄C₉H₄)₂ 0.88 47 Example rac-MS-3a-C100:1 200:1 Me PhMeNCH₂CH₂ (2-Me-7-PhC₉H₄)₂ 4.45 48 Example rac-MS-3b-C200:1 200:1 Me FcCH₂CH₂ (2-Me-7-PhC₉H₄)₂ 27.4 49 Example rac-MS-4a-C200:1 200:1 Me PhMeNCH₂CH₂ Flu₂ 12.2 50 Example rac-MS-4b-C 200:1 200:1Me FcCH₂CH₂ Flu₂ 14.1 51 Note: The unit of catalyst activity in Examples44-51 is 10⁶ g(PE) · mol⁻¹(Zr) · h⁻¹. According to the data in Table 4:1)When the substituent on the bridging atom in the metallocene compoundcontains an amine-substituted C₂ group or a metallocene-substituted C₂group, the prepared catalyst has higher catalytic activity for thepolymerization of ethylene. 2)The polymerization activity of thecatalyst can be further optimized by adjusting the test conditions suchas Al/Zr ratio of the catalyst and/or the Al/Zr ratio of thepolymerization system, as illustrated by Examples 44-45.

TABLE 5 Polymerization product property Catalyst Reaction Melting ratioratio Metallocene compound Catalyst PDI Isotacticity point Item CatalystAl/Zr Al/Zr R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) activity Mn Mw value(%) (° C.) Example rac-MS-1b- 200:1  500:1 Me PhMeNCH₂CH₂ (2-Me-7-p- 9.2133945 342375 2.57 99.3 157.63 52 C tBuC₆H₄C₉H₄)₂ Example rac-MS-1j-200:1  200:1 Me FcCH₂CH₂ (2-Me-7-p- 4.33 127361 36.431 2.83 98.6 152.353 C tBuC₆H₄C₉H₄)₂ Example rac-MS-1b- 200:1  549:1 Me PhMeNCH₂CH₂(2-Me-7-p- 33.7 173453 394257 2.273 99.1 154.4 54 C tBuC₆H₄C₉H₄)₂Example rac-MS-1b- 200:1  549:1 Me PhMeNCH₂CH₂ (2-Me-7-p- 154 135427397892 2.938 98.4 153.2 55 C tBuC₆H₄C₉H₄)₂ Example rac-MS-1j- 200:11707:1 Me FcCH₂CH₂ (2-Me-7-p- 43.7 82451 213509 2.59 96.7 150.2 56 CtBuC₆H₄C₉H₄)₂ Note: In Table 5, the unit of catayst activity in Examples52-58 is 10⁶ g(PP) · mol⁻¹(Zr) · h⁻¹. According to the data in Table 5:1)When the substituent on the bridging atom in the metallocene compoundcontains an amine-substituted C₂ group or a metallocene-substituted C₂group, the prepared catalyst has higher catalytic activity for thepolymerization of propylene.. 2)The polymerization activity of thecatalyst can be further optimized by adjusting the test conditions suchas Al/Zr ratio of the catalyst and/or the Al/Zr ratio of thepolymerization system, as illustrated by Examples 52, 54, and 56.

TABLE 6 Catalyst Reaction Metallocene Compound Catalyst Item CatalystAl/Zr ratio Al/Zr ratio R^(I) R^(II) (Cp^(III))_(n)(E)_(2−n) activityExample 57 rac-MS-3c-C 200:1 1200:1 Me PhMeN(CH₂)₅ (2-Me-7-PhC₉H₄)₂ 152Example 58 rac-MS-3d-C 200:1 1200:1 Me PhMeN(CH₂)₈ (2-Me-7-PhC₉H₄)₂ 147Example 59 rac-MS-3e-C 200:1 1200:1 Me PhMeN(CH₂)₁₂ (2-Me-7-PhC₉H₄)₂ 159Example 60 rac-MS-3f-C 200:1 1200:1 Me PhMeN(CH₂)₁₅ (2-Me-7-PhC₉H₄)₂ 136Example 61 rac-MS-3g-C 200:1 1200:1 Me p-ClC₆H₄MeN(CH₂)₅(2-Me-7-PhC₉H₄)₂ 125 Example 62 rac-MS-3h-C 200:1 1200:1 Mep-MeOC₆H₄MeN(CH₂)₅ (2-Me-7-PhC₉H₄)₂ 135 Example 63 rac-MS-3i-C 200:11200:1 Me Fc(CH₂)₅ (2-Me-7-PhC₉H₄)₂ 143 Example 64 rac-MS-3j-C 200:11200:1 Me Fc(CH₂)₈ (2-Me-7-PhC₉H₄)₂ 138 Example 65 rac-MS-3k-C 200:11200:1 Me Fc(CH₂)₁₂ (2-Me-7-PhC₉H₄)₂ 141 Example 66 rac-MS-3l-C 200:11200:1 Me Fc(CH₂)₁₈ (2-Me-7-PhC₉H₄)₂ 127 Example 67 rac-MS-3p-C 200:11200:1 Me Fc(CH₂)₅ (4-Ph-2-MeC₉H₄)(NtBu) 114 Comparative rac-MS-3m-C200:1 1200:1 Me nBu (2-Me-7-PhC₉H₄)₂ 138 Example 1 Comparativerac-MS-3n-C 200:1 1200:1 Me n-CH₃(CH₂)₇ (2-Me-7-PhC₉H₄)₂ 136 Example2Example 67 rac-MS-3o-C 200:1 1200:1 Me H (4-Ph-2-MeC₉H₄)(NtBu) 86.8Note: In Table 6, the unit of catalyst activity in Examples 57-67 is 10⁶g(PP) · mol⁻¹(Zr) · h⁻¹. ″--″ means there is no such data.

According to the data in Table 6:

When the substituent on the bridging atom in the metallocene compound isa C₅-C₁₅ group substituted with an amine group or a C₅-C₁₅ groupsubstituted with a metallocene group, the prepared catalyst has highercatalytic activity for the polymerization of propylene.

According to the data in Tables 1-6:

Compared with the substituent on the bridging atom in the metallocenecompound that do not contain an amine-substituted group or ametallocene-substituted group, when the substituent on the bridging atomin the metallocene compound is the amine-substituted group or themetallocene-substituted group, the prepared catalyst has highercatalytic activity for the polymerization of propylene.

1. A metallocene compound, having a structure as shown in formula (I):R^(I)R^(II)Z(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V)   formula (I) wherein informula (I), R^(I) and R^(II) are the same or different, and at leastone of R^(I) and R^(II) is selected from amino-substituted C₁-C₂₀hydrocarbyl, amino-substituted C₁-C₂₀ halohydrocarbyl, amino-substitutedC₁-C₂₀ alkoxy, and amino-substituted C₆-C₂₀ phenolic group; and/or atleast one of R^(I) and R^(II) is selected from metallocenegroup-substituted C₁-C₂₀ hydrocarbyl, metallocene group-substitutedC₁-C₂₀ halohydrocarbyl, metallocene group-substituted C₁-C₂₀ alkoxy, andmetallocene group-substituted C₆-C₂₀ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene group substituted byC₁-C₂₀ hydrocarbyl, C₁-C₂₀ halohydrocarbyl, C₁-C₂₀ alkoxy or C₆-C₂₀phenolic group; Z is selected from carbon, silicon, germanium, and tin;Cp^(III) is cyclopentadienyl containing or not containing a substituent,indenyl containing or not containing a substituent, or fluorenylcontaining or not containing a substituent, as shown in formula (II),wherein R^(i), R^(ii), and R^(iii) are substituents in the correspondingrings;

R^(i), R^(ii) and R^(iii) are the same or different, and eachindependently selected from hydrogen, and linear or branched, saturatedor unsaturated C₁-C₂₀ hydrocarbyl with or without a heteroatom; E isNR^(iv) or PR^(iv); R^(iv) is selected from hydrogen and linear orbranched, saturated or unsaturated C₁-C₂₀ hydrocarbyl with or without aheteroatom; M is selected from IVB group metals; L^(IV) and L^(V) arethe same or different, and each independently selected from hydrogen andlinear or branched, saturated or unsaturated C₁-C₂₀ hydrocarbyl with orwithout a heteroatom; and n is 1 or
 2. 2. The metallocene compoundaccording to claim 1, wherein the amino is as shown in formula (III):

wherein in formula (III), R_(a) and R_(b) are the same or different, andeach independently selected from hydrogen, C₁-C₆ alkyl, C₆-C₁₈ aryl,C₇-C₂₀ arylalkyl, and C₇-C₂₀ alkylaryl, preferably from C₁-C₆ alkyl,C₆-C₁₂ aryl, and C₇-C₁₀ arylalkyl, more preferably from C₁-C₄ alkyl,phenyl, and C₇-C₉ arylalkyl; and/or the metal in the metallocene groupis Fe, preferably, the metallocene group is ferrocenyl.
 3. Themetallocene compound according to claim 1, wherein in formula (I), R^(I)and R^(II) are the same or different, and at least one of R^(I) andR^(II) is selected from amino-substituted C₁-C₁₀ hydrocarbyl,amino-substituted C₁-C₁₀ halohydrocarbyl, amino-substituted C₁-C₁₀alkoxy, and amino-substituted C₆-C₁₀ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene group-substitutedC₁-C₁₀ hydrocarbyl, metallocene group-substituted C₁-C₁₀halohydrocarbyl, metallocene group-substituted C₁-C₁₀ alkoxy, andmetallocene group-substituted C₆-C₁₀ phenolic group; and/or at least oneof R^(I) and R^(II) is selected from metallocene group substituted byC₁-C₁₀ hydrocarbyl, C₁-C₁₀ halohydrocarbyl, C₁-C₁₀ alkoxy or C₆-C₁₀phenolic group; and/or in formula (II), R^(i), R^(ii) and R^(iii) arethe same or different, and each independently selected from hydrogen,C₁-C₂₀ hydrocarbyl, C₁-C₂₀ haloalkyl, C₆-C₂₀ aryl, C₆-C₂₀ haloaryl,C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₃-C₂₀ cycloalkyl, C₃-C₂₀heterocycloalkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀ alkoxy, C₆-C₂₀phenolic group, C₁-C₂₀ amino, and a group containing a heteroatomselected from groups 13 to 17; and/or R^(iv) is selected from hydrogenand linear or branched, saturated or unsaturated C₁-C₁₀ hydrocarbyl withor without a heteroatom; and/or in formula (I), M is selected from Ti,Zr and Hf; and/or in formula (I), L^(IV) and L^(V) are the same andselected from hydrogen, chlorine, ethyl, phenyl, benzyl, anddimethylamino.
 4. A preparation method of the metallocene compound ofclaim 1, wherein when n is 2, the preparation method comprises: S1.reacting a H₂(Cp^(III)) with an alkali metal-organic compound to form acorresponding [H(Cp^(III))]⁻ alkali metal salt; S2. reacting the[H(Cp^(III))]⁻ alkali metal salt with a R^(I)R^(II)ZX₂ to form aR^(I)R^(II)Z[H(Cp^(III))]₂; S3. reacting the R^(I)R^(II)Z[H(Cp^(III))]₂with an alkali metal-organic compound to form a correspondingR^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metal salt; S4. reacting theR^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metal salt with an X₂ML^(IV)L^(V) forsalt elimination reaction, to obtain aR^(I)R^(II)Z(Cp^(III))₂ML^(IV)L^(V); and when n is 1, the preparationmethod comprises: S1. reacting a H₂(Cp^(III)) and a H₂(E) with an alkalimetal-organic compound respectively, to form a corresponding[H(Cp^(III))]⁻ alkali metal salt and a corresponding [H(E)]⁻ alkalimetal salt; S2. reacting the [H(Cp^(III))]⁻ alkali metal salt and the[H(E)]⁻ alkali metal salt with a R^(I)R^(II)ZX₂ to form aR^(I)R^(II)Z[H(Cp^(III))][H(E)]; S3. reacting theR^(I)R^(II)Z[H(Cp^(III))][H(E)] with an alkali metal-organic compound toform a corresponding R^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt; S4.reacting the R^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt with anX₂ML^(IV)L^(V) for salt elimination reaction, to obtain aR^(I)R^(II)ZCp^(III) EML^(IV)L^(V); wherein X is selected from Cl, Brand I; preferably, in S4, the R^(I)R^(II)Z(Cp^(III))₂ ²⁻ alkali metalsalt or R^(I)R^(II)Z(Cp^(III))(E)²⁻ alkali metal salt, withoutseparation, directly reacts with the X₂ML^(IV)L^(V) for salt eliminationreaction.
 5. A preparation method of the metallocene compound of claim1, comprising: preparing the metallocene compound by carrying out a Zhydrogenation reaction between a precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) and a precursor of theR^(II); wherein the precursor of the R^(II) is a molecule containing amultiple bond, preferably, the molecule containing a multiple bond isselected from organic multiple bond molecules, CO and CO₂, wherein themultiple bond is selected from Groups 13 to 16 elements of the same ordifferent atoms, preferably is one or more bonds of C═C, C═C, C═N, C═N,C═O, C═P, N═N, C═S, C═C═C, C═C═N, C═C═O, and N═C═N.
 6. The preparationmethod according to claim 5, wherein the Z hydrogenation reaction iscarried out in the presence of a catalyst, and the catalyst is selectedfrom one or more of transition metal catalysts and Lewis acid catalysts,and preferably, one or more of platinum catalysts of the transitionmetal catalysts and B(C₆F₅)₃ catalysts of the Lewis acid; and/or, anamount of the catalyst used in the Z hydrogenation reaction is0.00001-50%, preferably 0.01-20% of the total mass of the reactants;and/or, a temperature of the Z hydrogenation reaction is −30 to 140° C.,preferably 0 to 90° C.; and/or, a reaction time of the Z hydrogenationreaction is greater than 0.1 h, preferably 2-50 h; and/or, the obtainedprecursor is separated or purified by recrystallization, and a solventfor the recrystallization is an aprotic solvent; preferably, the solventis one or more selected from linear or branched alkane compounds,cycloalkane compounds, aromatic hydrocarbons, halogenated hydrocarboncompounds, ether compounds, and cyclic ether compounds; furtherpreferably one or more of toluene, xylene, hexane, heptane, cyclohexane,and methylcyclohexane.
 7. The preparation method according to claim 5,wherein the precursor R^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) isprepared by one-pot method of chemical reaction; preferably, when n is2, the preparation method of the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) comprises: step 1), reactinga H₂(Cp^(III)) with an alkali metal-organic compound to form acorresponding [H(Cp^(III))]⁻ alkali metal salt; step 2), reacting the[H(Cp^(III))] alkali metal salt with a R^(I)HZX₂ to form aR^(I)HZ[H(Cp^(III))]₂; step 3), directly reacting theR^(I)HZ[H(Cp^(III))]₂ without separation, with aL^(viii)L^(viv)ML^(IV)L^(V) for eliminating a stable small moleculeL^(viii) or L^(viv), to obtain the precursorR^(I)HZ(Cp^(III))₂ML^(IV)L^(V); and/or, directly reacting theR^(I)HZ[H(Cp^(III))]₂ without separation, with an alkali metal-organiccompound to form an alkali metal salt; the obtained alkali metal salt isthen reacted with an X₂ML^(IV)L^(V) for salt elimination reaction, toobtain the precursor R^(I)HZ(Cp^(III))₂ML^(IV)L^(V); and when n is 1,the preparation method of the precursorR^(I)HZ(Cp^(III))_(n)(E)_(2-n)ML^(IV)L^(V) comprises: step 1), reactinga H₂(Cp^(III)) and a H₂(E) respectively with an alkali metal-organiccompound to form a corresponding [H(Cp^(III))]⁻ alkali metal salt and acorresponding [H(E)] alkali metal salt; step 2), reacting the[H(Cp^(III))]⁻ alkali metal salt and the [H(E)]⁻ alkali metal salt withR^(I)HZX₂ to form a R^(I)HZ[H(Cp^(III))][H(E)]; step 3), directlyreacting the R^(I)HZ[H(Cp^(III))][H(E)] without separation, with aL^(viii)L^(viv)ML^(IV)L^(V) by eliminating a stable small moleculeL^(viii) or L^(viv), to obtain the precursorR^(I)HZCp^(III)EML^(IV)L^(V); and/or, directly reacting theR^(I)HZ[H(Cp^(III))][H(E)] without separation, with an alkalimetal-organic compound to form an alkali metal salt; then reacting theobtained alkali metal salt with a X₂ML^(IV)L^(V) for salt eliminationreaction, to obtain the precursor R^(I)HZCp^(III)EML^(IV)L^(V); whereinX is selected from Cl, Br and I.
 8. The preparation method according toclaim 4, wherein in each step, a reaction temperature of the reaction isin a range from −100° C. to 140° C., preferably in a range from −85° C.to 110° C.; and/or, and a reaction time is more than 0.016 h, preferably2 to 100 h; preferably, in each step, reaction materials are mixed at atemperature of −100° C. to −20° C., preferably −85° C. to −10° C., andthe mixed reaction materials are reacted at 10° C. to 50° C., preferablyat 20° C. to 35° C. for 1 h to 100 h, preferably 5 h to 50 h.
 9. Thepreparation method according to claim 4, wherein in each step, thereaction is carried out in an aprotic solvent selected from one or moreof linear or branched alkane compounds, cycloalkane compounds, aromaticcompounds, halogenated hydrocarbon compounds, ether compounds and cyclicether compounds, preferably one or more of toluene, xylene,chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane,chloroform, tetrahydrofuran, ether, and dioxane; and/or the alkalimetal-organic compound is selected from hydrogenated metal, alkyl metal,alkenyl metal, aromatic metal, and amine metal, preferably alkyl metal,more preferably C₁-C₆ alkyl metal; and/or, the alkali metal is selectedfrom Li, Na and K, preferably Li.
 10. A catalyst for α-olefinpolymerization reaction, comprising: the metallocene compound of claim1, a cocatalyst, and a carrier.
 11. The catalyst according to claim 10,wherein the cocatalyst is selected from one or more of a Lewis acid, andan ionic compound containing a non-coordination anion and a Lewis acidor containing a non-coordination anion and a Bronsted acid cation;preferably, the Lewis acid comprises one or more of alkyl aluminum,alkyl aluminoxane, and organic borides; and/or the ionic compoundcontaining a non-coordination anion and a Lewis acid or containing anon-coordination anion and a Bronsted acid cation is selected fromcompounds containing 1-4 perfluoroaryl substituted borate anions. 12.The catalyst according to claim 11, wherein the alkyl aluminum comprisestrimethyl aluminum, triethyl aluminum, triisopropyl aluminum,tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum,tri-isoamyl aluminum, tri-n-amyl aluminum, tri-isohexyl aluminum,tri-n-hexyl aluminum, tri-isoheptyl aluminum, tri-n-heptyl aluminum,tri-isooctyl aluminum, tri-n-octyl aluminum, tri-isononyl aluminum,tri-n-nonyl aluminum, tri-isodecyl aluminum and tri-n-decyl aluminum;and/or the alkyl aluminoxane comprises methyl aluminoxane, ethylaluminoxane and butyl modified aluminoxane; and/or the organic boridecomprises trifluoroborane, triphenylborane, tris (4-fluorophenyl)borane, tris (pentafluorophenyl) borane, tris (3,5-difluorophenyl)borane and tris (2,4,6-trifluorophenyl) borane; and/or the perfluoroarylgroup is selected from perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, and perfluoroalkyl phenyl, and the cation is selected from n,n-dimethylphenylammonium ion, triphenylcarboonium ion, trialkyl ammoniumion, and triarylammonium ion.
 13. The catalyst according to claim 10,wherein in the catalyst, a content of the metallocene compound,calculated based on the M element, is 0.001 mass % to 10 mass %,preferably 0.01 mass % to 1 mass %; and/or a molar ratio of Al elementin the cocatalyst and M element in the metallocene compound is (1 to500):1, preferably (50 to 300):1.
 14. A preparation method of thecatalyst according to claim 10, comprises: combining the metallocenecompound, the cocatalyst, and the carrier under the action of a solventto form the catalyst, and preferably, a combining condition comprises: acombining temperature being −40° C. to 200° C., preferably 40° C. to120° C.; a combining time being greater than 0.016 h, preferably 2 h to100 h.
 15. The preparation method according to claim 14, wherein thesolvent is selected from one or more of linear hydrocarbons, branchedhydrocarbons, cyclic saturated hydrocarbons and aromatic hydrocarbons,preferably one or more of toluene, xylene, n-butane, n-pentane,isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane,n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptaneand neoheptane.
 16. A method for α-olefin polymerization carried out inthe presence of the metallocene compound according to claim
 1. 17. Themethod according to claim 16, wherein the polymerization reaction iscarried out without a solvent.
 18. The method according to claim 16,wherein conditions of the polymerization reaction comprises: reactiontemperature being −50° C. to 200° C., preferably 30° C. to 100° C.; andthe reaction time being 0.01 h to 60 h, preferably 0.1 h to 10 h,and/or, wherein relative to per gram of α-olefin, the usage of themetallocene catalyst or metallocene catalyst system is 0.001 mg to 1000mg, preferably 0.01 mg to 200 mg, more preferably 0.1 mg to 20 mg,and/or, wherein the α-olefin comprises C2-C20 α-olefin, preferablyC2-C14 α-olefin, more preferably ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-heptadiene, 1-octadecene and 1-eicosene, preferentially 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene or 1-tetradecene. 19-20. (canceled)21. The preparation method according to claim 7, wherein in each step, areaction temperature of the reaction is in a range from −100° C. to 140°C., preferably in a range from −85° C. to 110° C.; and/or, and areaction time is more than 0.016 h, preferably 2 to 100 h; preferably,in each step, reaction materials are mixed at a temperature of −100° C.to −20° C., preferably −85° C. to −10° C., and the mixed reactionmaterials are reacted at 10° C. to 50° C., preferably at 20° C. to 35°C. for 1 h to 100 h, preferably 5 h to 50 h.
 22. The preparation methodaccording to claim 7, wherein in each step, the reaction is carried outin an aprotic solvent selected from one or more of linear or branchedalkane compounds, cycloalkane compounds, aromatic compounds, halogenatedhydrocarbon compounds, ether compounds and cyclic ether compounds,preferably one or more of toluene, xylene, chlorobenzene, heptane,cyclohexane, methylcyclohexane, dichloromethane, chloroform,tetrahydrofuran, ether, and dioxane; and/or the alkali metal-organiccompound is selected from hydrogenated metal, alkyl metal, alkenylmetal, aromatic metal, and amine metal, preferably alkyl metal, morepreferably C₁-C₆ alkyl metal; and/or, the alkali metal is selected fromLi, Na and K, preferably Li.